WO1987005338A1 - Palladium-base electroless plating solution - Google Patents
Palladium-base electroless plating solution Download PDFInfo
- Publication number
- WO1987005338A1 WO1987005338A1 PCT/JP1987/000113 JP8700113W WO8705338A1 WO 1987005338 A1 WO1987005338 A1 WO 1987005338A1 JP 8700113 W JP8700113 W JP 8700113W WO 8705338 A1 WO8705338 A1 WO 8705338A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- plating solution
- palladium
- compound
- plating
- mol
- Prior art date
Links
- 238000007772 electroless plating Methods 0.000 title claims abstract description 38
- 239000000243 solution Substances 0.000 claims abstract description 170
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 72
- -1 amine compound Chemical class 0.000 claims abstract description 43
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 36
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011593 sulfur Substances 0.000 claims abstract description 22
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 150000002816 nickel compounds Chemical class 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 150000002941 palladium compounds Chemical class 0.000 claims abstract description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 108
- 229910052763 palladium Inorganic materials 0.000 claims description 48
- 150000004985 diamines Chemical class 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims description 6
- 229920000768 polyamine Polymers 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- 150000003568 thioethers Chemical class 0.000 claims description 3
- 150000002019 disulfides Chemical class 0.000 claims description 2
- 150000003256 radium compounds Chemical class 0.000 claims description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 2
- APVPOHHVBBYQAV-UHFFFAOYSA-N n-(4-aminophenyl)sulfonyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NS(=O)(=O)C1=CC=C(N)C=C1 APVPOHHVBBYQAV-UHFFFAOYSA-N 0.000 claims 1
- 150000003557 thiazoles Chemical class 0.000 claims 1
- 238000007747 plating Methods 0.000 abstract description 194
- 229910010277 boron hydride Inorganic materials 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 29
- 239000007788 liquid Substances 0.000 description 29
- 230000008021 deposition Effects 0.000 description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 17
- 229910052802 copper Inorganic materials 0.000 description 16
- 239000010949 copper Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
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- 238000000034 method Methods 0.000 description 12
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- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical compound OC(=O)CSCC(O)=O UVZICZIVKIMRNE-UHFFFAOYSA-N 0.000 description 10
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- 239000002184 metal Substances 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 6
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- 230000003197 catalytic effect Effects 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
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- 230000000704 physical effect Effects 0.000 description 4
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 3
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- 238000005452 bending Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
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- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
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- 239000003381 stabilizer Substances 0.000 description 3
- 235000019303 thiodipropionic acid Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- BHQCQFFYRZLCQQ-OELDTZBJSA-N cholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 BHQCQFFYRZLCQQ-OELDTZBJSA-N 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
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- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
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- 239000011135 tin Substances 0.000 description 2
- JIVZKJJQOZQXQB-UHFFFAOYSA-N tolazoline Chemical compound C=1C=CC=CC=1CC1=NCCN1 JIVZKJJQOZQXQB-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XRLUJVFOGKUSMQ-ZVGUSBNCSA-L (2r,3r)-2,3-dihydroxybutanedioate;nickel(2+) Chemical compound [Ni+2].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O XRLUJVFOGKUSMQ-ZVGUSBNCSA-L 0.000 description 1
- BHQCQFFYRZLCQQ-UHFFFAOYSA-N (3alpha,5alpha,7alpha,12alpha)-3,7,12-trihydroxy-cholan-24-oic acid Natural products OC1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 BHQCQFFYRZLCQQ-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- UPPLJLAHMKABPR-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;nickel(2+) Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O UPPLJLAHMKABPR-UHFFFAOYSA-H 0.000 description 1
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 description 1
- FYWDUQCSMYWUHV-UHFFFAOYSA-N 3-chloro-5-hydroxypentan-2-one Chemical compound CC(=O)C(Cl)CCO FYWDUQCSMYWUHV-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004380 Cholic acid Substances 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- FFDGPVCHZBVARC-UHFFFAOYSA-N N,N-dimethylglycine Chemical compound CN(C)CC(O)=O FFDGPVCHZBVARC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910003322 NiCu Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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- 229910052770 Uranium Inorganic materials 0.000 description 1
- DOIXGGGORNAJAT-UHFFFAOYSA-M [NH4+].[Ni+].[O-]S([O-])(=O)=O Chemical compound [NH4+].[Ni+].[O-]S([O-])(=O)=O DOIXGGGORNAJAT-UHFFFAOYSA-M 0.000 description 1
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- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
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- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- ALWUDBGJBKUAME-UHFFFAOYSA-N palladium;sodium;hydrochloride Chemical compound [Na].Cl.[Pd] ALWUDBGJBKUAME-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
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- NEUOBESLMIKJSB-UHFFFAOYSA-J tetrasodium;tetraacetate Chemical compound [Na+].[Na+].[Na+].[Na+].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O NEUOBESLMIKJSB-UHFFFAOYSA-J 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- 210000002105 tongue Anatomy 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/24—Reinforcing the conductive pattern
- H05K3/244—Finish plating of conductors, especially of copper conductors, e.g. for pads or lands
Definitions
- the present invention relates to a palladium electroless plating solution.
- the electrical contact portions of electronic components be coated with a noble metal having high corrosion resistance and excellent electrical characteristics.
- gold electrical plating is mainly used as the surface coating of electrical contact parts, but it is not possible to apply a uniform thickness coating to electronic components with fine and complicated shapes by the electrical plating method. Have difficulty.
- the electroless plating method it is possible to form a uniform deposited film even on a component having a fine and complicated shape.
- the development of a surface treatment method is desired.
- palladium is the cheapest of the platinum group metals, and is expected to have a wide range of industrial applications.
- an electroless palladium plating solution a divalent palladium salt as a metal source, ammonia as a complexing agent, ethylenediaminetetraacetic acid or a salt thereof as a stabilizer, and hydrazine as a reducing agent.
- the aqueous solution used was typical.
- this solution has a serious drawback that it cannot be stored because of its poor stability and easy decomposition.
- the Pd of the pretreatment liquid is immediately decomposed by bringing in the Pd.
- any of the above-mentioned plating liquids cannot be applied to electronic components because the resulting plating film has many cracks and poor solderability.
- the plating speed becomes extremely slow, and the plating film becomes black and the appearance becomes poor. Therefore, the electroless palladium plating solution that has been reported to date has not yet reached the laboratory scale.
- a known electroless Pd—Ni alloy plating solution includes nickel sulfate 0.11 mol, palladium chloride 0.11 mol 3, 38% hydrochloric acid 4 ⁇ 2, 25% ammonium chloride.
- Monitor water 1 60 mQ / S, sodium hypophosphite
- An object of the present invention is to provide a palladium-based electroless plating solution that can be used on an industrial scale.
- Another object of the present invention is to provide a palladium-based electroless plating solution having excellent stability and good appearance of a deposited film.
- Still another object of the present invention is to provide a palladium electroless plating solution having a low porosity of a deposited film, good corrosion resistance, good adhesion to a substrate, and the like.
- Still another object of the present invention is to provide a palladium-based electroless plating solution having good workability and easy liquid management.
- Still another object of the present invention is to provide a palladium-based electroless plating solution capable of forming a plating film with few cracks and good solderability.
- Still another object of the present invention is to provide a palladium-based electroless plating solution capable of forming a Pd—Ni alloy plating film with little decrease in the surface properties of a deposited film even in an organic gas atmosphere. It is in.
- the present invention provides the following palladium electroless plating solution.
- a palladium-based electroless plating solution characterized by being composed of an aqueous solution containing.
- a palladium-based electroless plating solution characterized by being composed of an aqueous solution containing.
- the palladium-based electroless plating solution of the present invention is a completely new method in which at least one of ammonia and an amine compound and an organic compound containing divalent sulfur are used in combination as a stabilizer. Things.
- a palladium-based electroless plating solution is extremely excellent in stability, and can form a palladium-based plating film having good appearance and physical properties.
- palladium chloride palladium sodium chloride, palladium chloride, palladium ammonium chloride, palladium sulfate, palladium nitrate, palladium acetate, palladium acetate are used as the Pd supply source.
- a palladium compound such as palladium is used.
- the concentration of the palladium compound should be about 0.0001 to 0.5 mol 2, preferably about 0.001 to 0.1 mol. However, it is not practical because the deposition rate becomes slower. On the other hand, when the concentration exceeds 0.5 mol, the precipitation rate is not further improved and the stability of the plating solution is further impaired. Not good.
- the plating solution of the present invention in order to maintain the stability of the solution, at least one of ammonia and an amide compound is added to the divalent solution. It is necessary to use in combination with a sulfur-containing organic compound.
- the ammonia and amine compounds form a complex with Pd in the plating solution to stably maintain these components in the solution and contribute to the stabilization of the solution.
- the concentration of the ammonia and / or the amine compound is about 0.001 to 8 mol S, preferably about 0.01 to 5 mol. When using ammonia alone, it is more preferable to use about 0.075 mol or more in order to improve the stability of the plating solution.
- the higher the concentration of ammonia and / or amine compound the better the stability of the liquid.However, if the concentration exceeds the above range, it is uneconomical, especially when using ammonia, the working environment is poor due to odor etc. I don't like it. On the other hand, if the concentration is below the above range, the stability of the solution is reduced, and the plating solution is easily decomposed.
- the amide compound also includes amic acids.
- the amide compounds suitable for use in the present invention include monoamines such as methylamine, ethylamine, propylamine, dimethylamine, and trimamine. Chilamin, dimethylethylamine, benzylamine, 2-naphthylamine, isoptilamine, isoaminoleamine, etc. Polyamines such as diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, etc.
- Amino acids such as oxaethyleneheptamine, ethylenediaminetetraacetic acid or its sodium salt, N-hydroxyethylenediaminetriacetic acid or its sodium salt, Imidazolin, 2-methyl-2-imid as imidazolines, such as syn, N-methyldaricin, dimethylglycine, iminodiacetic acid, hydantoic acid, and glycosamine.
- At least one compound of ammonia and an amine compound one selected from ammonia, diamines and polyamines can be preferably used.
- At least one of the above-described amide compounds and pendants may be used, but ammonia alone is used.
- the time until the initial generation of the plating that is, the time until the plating starts to be adhered after the object to be plated is immediately immersed in the plating liquid may be increased.
- the initial generation time can be reduced by using the ammonia and the above-mentioned amine compound in combination.
- the divalent sulfur-containing organic compound suitable for use in the present invention includes, specifically,
- sulfur-containing organic compounds can be used alone or in appropriate combination.
- the amount of the sulfur-containing organic compound to be used is about 1 to 500 mgZS, preferably about 5 to 10 OfflgZG.
- the use amount of the sulfur-containing organic compound exceeds the above range, the deposition rate of the plating film is reduced, and the appearance of the deposited plating film is also deteriorated. Not good. Concentrations below the above range are not suitable because the stability of the plating solution becomes insufficient.
- the plating solution of the present invention requires the use of ammonia and / or an amine compound and a sulfur-containing organic compound in an essential manner, and is extremely stable on an industrial scale. It is a plating solution suitable for use.
- a hypophosphorous acid compound and a borohydride compound is used as a reducing agent for reducing metal ions.
- hypophosphorous acid compound hypophosphorous acid or its ammonium, lithium, sodium, potassium, calcium salt and the like can be used
- borohydride compound dimethylethyl is used.
- Aminboranes such as uranium, trimethylamine, isopropylamine, morpholine borane and the like, sodium borohydride, potassium borohydride and the like can be used.
- the amount of the reducing agent used is about 0.05 to 1 mol ⁇ , preferably about 0.1 to 0.5 mol. Consumption
- the amount is less than 0.05 mol ZS, the plating is not sufficiently precipitated, and if it exceeds 1 mol, the plating solution becomes unstable, which is not preferable.
- the plating solution of the present invention is obtained by using ammonia in combination with a specific sulfur-containing organic compound. It is extremely excellent in stability, and therefore various reducing agents can be used as described above.
- the palladium-based electroless plating solution of the present invention comprises: a) a palladium compound, b) at least one of ammonia and an amine compound, c) an organic compound containing divalent sulfur, and d) ) At least one of a hypophosphorous acid compound and a borohydride compound;
- Pd plating solution Is dissolved in water to form an aqueous solution (hereinafter referred to as a Pd plating solution), which has good liquid stability and can form a Pd plating film with excellent appearance and physical properties. it can.
- a palladium-based electroless plating solution capable of forming a palladium-nickel alloy plating film by further adding a nickel compound to the plating solution. Liquid
- the electroless plating solution (Pd—Ni plating solution) to which such a nickel compound is added has the same excellent stability as the above-mentioned Pd plating solution, and the P The d—Ni alloy plating film has the same excellent appearance and physical properties as the plating film of Pd alone obtained by the Pd plating solution.
- Nickel compounds suitable for use in the Pd—Ni plating solution of the present invention include nickel chloride and nickel chloride. Monium, Nickel bromide, Nickel iodide, Nickel sulfate, Nickel sulfate ammonium, Nickel nitrate, Nigel carbonate, Nickel sulfamate, Nickel acetate, Nickel benzoate, Nickel citrate, Nickel formate, Nickel tartrate And nickel oxalate.
- concentration of the nickel compound is about 0.01 to 1 mol / S, and preferably about 0.01 to 0.5 mol.
- the concentration is less than 0.01 mol Z 2
- nickel is difficult to precipitate, whereas if the concentration is higher than 1 molno S, the stability of the plating solution is reduced, and ammonia and / or It is necessary to add a large amount of an amine compound, which is uneconomical. In particular, when ammonia is used, it is not preferable because the working environment is deteriorated due to odor and the like.
- components other than the nickel compound may be the same as the Pd plating solution in terms of the type and amount of the compound used.
- the ratio of palladium to nickel in the Pd—Ni alloy plating film deposited from the Pd-Ni plating solution is determined by the concentration ratio of the palladium compound to the nickel compound in the Pd—Ni plating solution. Can be adjusted by changing the thickness of the film, and a paint film having an arbitrary composition can be easily obtained.
- the palladium electroless plating solution of the present invention is obtained by dissolving each of the active ingredients described above in water to form an aqueous solution. In the plating solution, it is not essential to adjust the pH, but in the case of the Pd plating solution, it is preferable to adjust 11 to about 5 to 10 and the Pd—Ni plating solution. Then, it is preferable to adjust the pH to about 5 to 11.
- P H adjustment of main luck solution may be performed by Kiyoshie if HCS, H 2 S 0 acid and N a 0 H such alkali compounds such as 4.
- the plating solution of the present invention can be plated at a wide temperature range of about 10 to 90, and particularly 25 to 70 °. At a liquid temperature of about C, a smooth and glossy best paint film can be obtained. As described above, the plating can be performed even at a relatively low temperature, so that the control of the plating solution can be easily performed. In particular, when ammonia is used, the volatilization of ammonia can be suppressed. Can be kept good. In the plating liquid of the present invention, the higher the liquid temperature, the more the plating film There is a tendency for the precipitation rate to increase, and an arbitrary deposition rate can be obtained by appropriately setting the temperature within the above-mentioned temperature range.
- the deposition rate of the plating film depends not only on the temperature of the solution but also on the concentration of the metal component, but it has almost no effect on the fluctuation of the concentration of other components divided by the pH of the plating solution. Do not receive. Therefore, in the plating solution of the present invention, the thickness of the plating film can be easily controlled by adjusting the concentration of the metal component and the temperature of the plating solution.
- the substrate which has a catalytic property for the reductive deposition of the Ni film.
- the catalytic substrate include Fe, Co, NiCu, Sn, Ag, Au, Pt, Pd, and alloys thereof.
- non-catalytic substrates such as resin, glass, ceramics, and W can be provided with a catalytic property by a known method such as, for example, a sensitizing activator method or a catalytic catalyzer method.
- the plating process can be performed by immersion in the plating solution as in the above method.
- the deposition of the palladium film or the palladium nickel alloy film by the plating solution of the present invention proceeds autocatalytically. Therefore, a film having low porosity and high adhesion can be obtained.
- the electroless palladium plating liquid of the present invention has the following excellent properties.
- the stability of the plating solution is good, so it can be used with a low amount of ammonia and can suppress the volatilization of ammonia.
- the amine compound does not volatilize during the plating operation or during storage. Therefore, the storage stability of the plating solution is good, and the working environment is also good.
- the deposition rate depends only on the metal concentration and the solution temperature, and is hardly affected by the concentration of other components or the pH of the solution, so that control of the plating film thickness is easy. ⁇ ⁇ By setting the pH to near neutrality, the types of objects to be treated, resist tongues, etc. that can be used are increased, and various types of plating equipment can be used.
- the plating bath of the present invention is a palladium-based electroless plating solution having excellent characteristics as described above, and is applied to contact parts requiring high reliability in electronic parts, and to a gold plating film. It is extremely useful for application as a base plating film for prolonging the service life, and can be widely used for other parts, especially those requiring corrosion resistance.
- Fig. 1 is a graph showing the relationship between plating time and the thickness of the deposited plating film in the Pd plating solution
- Fig. 2 is a graph showing Ni and P in the Pd-Ni plating solution
- Fig. 3 is a graph showing the relationship between the ratio of d and the amount of Ni in the precipitate
- Fig. 3 is a graph showing the relationship between plating time and the amount of precipitation in the Pd-Ni plating solution
- Fig. 4 is P
- Fig. 5 is a graph showing the relationship between the liquid temperature and the deposition rate in the d-Ni plating solution.
- Fig. 5 is a graph showing the relationship between the liquid temperature in the Pd-Ni plating solution and the amount of Ni in the precipitate. It is.
- composition plating solution was prepared.
- plating was performed on the copper plate at two temperatures, 3 CTC and 40.
- the relationship between plating film thickness and plating time A graph of the relationship is shown in FIG.
- the obtained paint film was subjected to a bending test, and as a result, the adhesion was extremely good.
- a thick coating film was formed by performing the plating for 6 hours, a glossy silver-white film having a good appearance was obtained.
- the plating solution of the present invention shown in Example 1 was prepared to each ⁇ value shown in Table 2 below (using HCS), and a plating film having a thickness of 1 m was formed on a copper plate at a liquid temperature of 40 ° C. .
- the unadjusted paint solution had a pH of 11.5. After observing the state of the obtained paint film with a scanning electron microscope (3000 magnification), a solderability test was performed by the following method. Table 2 shows the results.
- the adhered surface of carbon is less than 98%, and the adhered state is not uniform.
- Example 2 Using the same plating bath as in Example 1, plating was performed on the copper plate, and the copper plate was immersed in the plating solution, except that the EDTA ⁇ 2 Na amount was changed to the variable shown in Table 3 below. After, no ,. The time until the precipitation of the radim, that is, the initial generation time, was determined. Table 3 shows the results.
- composition plating solution was prepared. opdc ⁇ 2 ⁇ . 0 1 mol zso NH 2 CH 2 CH 2 NH 2 0.08 mol / S o-thiodiglycolic acid 20 nig / ⁇
- the temperature of the solution was 60 using this plating solution.
- C was plated on a copper plate.
- the pH of the plating solution was 11.0.
- the deposition rate was 1,41 mZhr, and a linear relationship was observed between the amount of deposition and the time, confirming that autocatalytic deposition was performed.
- the appearance of the obtained plating film was good.
- a bending test was performed on this sample in accordance with JIS-Z-2248, and there was no abnormality and the adhesion of the plating film was good.
- Example 4 The plating solution shown in Example 4 was adjusted to the respective pH values shown in Table 4 below with HCS, and a plating film having a thickness of 1 ⁇ m was formed on a copper plate at a solution temperature of 60. For each of the obtained plating films, the appearance of the plating and the solderability test were performed in the same manner as in Example 2. The results are shown in Table 4. the 4th
- composition plating solution was prepared.
- the dimethylamines include dimethylamine, dimethylethylamine, methylylenediamine, tetramethylethylenediamine, diethyltriamine, and pentaethyleneimide.
- Samin, N-hydroxyethylenediamine triacetic acid, glycine, imidazoline, and 2-benzyl-2-imidazoline were used alone.
- plating solutions were adjusted to pH 8 with hydrochloric acid, and the temperature of the solution was 6 ml.
- Plating was performed on the copper foil. As a result, a film with good adhesion and appearance was formed. The obtained metal coating had no cracks and good solderability. Further, the stability of each of the above-mentioned plating liquids during heating and storage stability was examined, and as a result, good stability was shown.
- a plating solution having the following composition was prepared.
- the plating solution was adjusted to pH 8 with hydrochloric acid, and plating was performed on a copper plate at a solution temperature of 6 ° C. As a result, a film having good adhesion and appearance was formed. The obtained paint film was free of cracks and had good solderability. Further, the stability of the above-mentioned plating liquids during heating and storage stability were examined, and good stability was shown.
- a plating solution having the following composition was prepared.
- dimethylamine, isopropylamine, morpholine and sodium borohydride were used alone.
- the plating solution was adjusted to pH 8 with hydrochloric acid, and plating was performed on a copper plate at a solution temperature of 60 ° C. As a result, a film having good adhesion and appearance was formed. The obtained paint film was free of cracks and had good solderability. Further, the stability of the above-mentioned plating liquids during heating and storage stability were examined, and good stability was shown.
- Example 9 A plating solution having the following composition was prepared.
- Ni CS 2 * 613 20 was changed in six ways: 0.005, 0.01, 0.02, 0.05, 0.1 and 0.2 mol.
- FIG. 2 shows the relationship between the ratio of Ni and Pd in the plating solution and the amount of Ni in the precipitate.
- a precipitate having an arbitrary composition can be obtained by adjusting the ratio of Ni and Pd in the plating solution.
- the appearance of the obtained precipitate was good, and as a result of performing a bending test according to JIS-Z-2248, no abnormality occurred in all samples, and the adhesion was good.
- Table 5 shows the results of closed storage in C and open storage in 25.
- thiodiglycolic acid was not contained, and the other components contained the same plating solution as the above-mentioned plating solution.
- the plating solution of the present invention is excellent in stability at high temperatures and long-term storage at room temperature.
- the solution was decomposed in 4 to 7 days, which is an excellent result compared to the conventional plating solution.
- the decomposition of the plating solution due to the open storage is caused by the volatilization of the ammonia, and a long-time open storage is possible by appropriately supplementing the ammonia.
- a plating solution having the following composition was prepared.
- N i of precipitates, when using N a H 2 P 0 ⁇ H 2 0 is about 30 wt%, in the case of using N a BH 4 is about 35 wt% In I got it.
- a plating solution having the following composition was prepared.
- sulfur-containing organic compound three kinds of thiodiglycolic acid, thiodipropionic acid and 2-mercaptobenzothiazole were used.
- Fig. 4 shows the relationship between the liquid temperature and the deposition rate when plating was performed on a copper plate for 1 hour by changing the liquid temperature using this plating liquid.
- Fig. 5 shows the relationship between the liquid temperature and the amount of Ni in the precipitate.
- the symbol ⁇ indicates the results when thiodiglycolic acid was used
- the symbol ⁇ indicates the results when thiodipropionic acid was used
- the symbol ⁇ indicates the results when 2-mercaptobenzothiazole was used. From the above results, it can be seen that the higher the liquid temperature, the higher the plating speed and the higher the amount of N 1 in the deposit.
- the obtained paint film had a good appearance when any of thiodiglycolic acid, thiodipropionic acid and 2-mercaptobenzothiazole was used.
- Example 1 2 shows the relationship between the liquid temperature and the deposition rate when plating was performed on a copper plate for 1 hour by changing the liquid temperature using this plating liquid.
- Fig. 5 shows the
- a plating solution having the following composition was prepared.
- the plating solution shown in Example 12 was prepared at each pH value shown in Table 6 below with HCS and Na0H, and a plating film having a thickness of 1 m was formed on a copper plate at a solution temperature of 40. .
- the condition of the paint film and the solderability test, and the plating speed were measured. The results are shown in Table 6. 6
- a plating solution having the following composition was prepared.
- Diamines such as dimethylamine, dimethylethylamine, methylamine, and tetramethylamine Amide, diethylenamine, pentaethylenehexamine, N-hydroxyethylenediamintriacetic acid, glycine, imidazoline, and 2-benzyl-2-imine Dazolin was used alone.
- a plating solution having the following composition was prepared.
- N a H 2 is set to P 0 a ⁇ H 2 0 0. 06 mol / S sulfur-containing organic compounds, HSCH 2 COOH, SH
- the plating solution was adjusted to pH 8 with hydrochloric acid, and plating was performed on a copper plate at a solution temperature of 6 ° C. As a result, a film having good adhesion and appearance was formed. The resulting paint film was free of cracks and had good solderability. Further, the stability of each of the above plating liquids upon heating and storage stability were examined, and good stability was shown.
- a plating solution having the following composition was prepared.
- Dimethylamine, isopropylamine, morpholine, and sodium borohydride were used alone as the reducing agents.
- plating liquids were adjusted to ⁇ 8 with hydrochloric acid, and plated at 6 ° C. on a copper plate. As a result, a film having good adhesion and appearance was formed. The obtained plating film Had no cracks and good solderability. Further, the stability of each of the above plating liquids upon heating and storage stability were examined, and good stability was shown.
Abstract
An electroless plating solution excellent in stability and capable of forming a good palladium-base plating layer, which comprises an aqueous solution containing a) a palladium compound, b) at least one of ammonia and an amine compound, c) an organic compound containing divalent sulfur, and d) at least one of hypophosphorous compound and boron hydride compound. The solution may further contain a nickel compound.
Description
明 細 書 Specification
パラジゥム系無電解メ ツキ液 Palladium electroless plating solution
技術分野 Technical field
本発明は、 パラジウム系無電解メ ツキ液に関する。 The present invention relates to a palladium electroless plating solution.
背景技術 Background art
電子部品の電気接点部分には、 耐食性が高く 、 かつ電 気的特性のすぐれた貴金属による表面被覆を施すご とが 要求されている。 現在、 電気接点部分の表面被覆と して は、 主として、 金の電気メ ツキが採用されているが電気 メ ツキ法では微細で複雑な形状の電子部品に均一な厚さ の被覆を施すことは困難である。 It is required that the electrical contact portions of electronic components be coated with a noble metal having high corrosion resistance and excellent electrical characteristics. At present, gold electrical plating is mainly used as the surface coating of electrical contact parts, but it is not possible to apply a uniform thickness coating to electronic components with fine and complicated shapes by the electrical plating method. Have difficulty.
これに対して、 無電解メ ツキ法によれば、 微細で複雑 な形状の部品に対しても、 均一な析出皮膜を形成させる ことが可能であり、 このため無電解メ ツキ法による貴金 属の表面処理方法の開発が望まれている。 特にパラジゥ ムは白金族金属の中で、 最も安価であり、 広い範囲での 工業的応用が期待-されている。 On the other hand, according to the electroless plating method, it is possible to form a uniform deposited film even on a component having a fine and complicated shape. The development of a surface treatment method is desired. In particular, palladium is the cheapest of the platinum group metals, and is expected to have a wide range of industrial applications.
従来、 無電解パラジゥムメ ツキ液としては、 金属源と して 2価のパラジウム塩、 錯化剤と してアンモニア、 安 定剤と してエチレンジア ミ ン四酢酸またはその塩、 還元 剤としてヒ ドラジンを用いる水溶液が代表的なものであ つた。
しかしこの溶液は安定性が悪く 、 自然分解しやすいた め保存ができないという大きな欠点を有している。 また, 前処理液の P dの持ち込みにより、 すぐに分解するとい う欠点もある。 しかもこの様なヒ ドラジンを還元剤と し て使用するメ ツキ液では、 長時間被メ ツキ物をメ ツキ液 に浸漬すると、 メ ツキ液中の有効成分がまだ少ししか消 費されていないにもかかわらず析出速度が著しく低下す るという欠点もある。 更にメ ツキ液の安定性が悪いこと から、 錯化剤であるア ンモニアの濃度を高く することが 必要であり、 作業環境上好ま しく ないという問題点もあ また、 2価のパラジウム塩、 エチレンジァ ミ ン四酢酸 塩、 エチレンジア ミ ン、 及び次亜リ ン酸ソ一ダからなる 無電解パラジウムメ ツキ液も知られているが （特公昭 4 6— 2 6 7 6 4 ) 、 このメ ツキ液も安定性が悪く 、 短時 間で分解するという欠点がある。 Conventionally, as an electroless palladium plating solution, a divalent palladium salt as a metal source, ammonia as a complexing agent, ethylenediaminetetraacetic acid or a salt thereof as a stabilizer, and hydrazine as a reducing agent. The aqueous solution used was typical. However, this solution has a serious drawback that it cannot be stored because of its poor stability and easy decomposition. In addition, there is also a disadvantage that the Pd of the pretreatment liquid is immediately decomposed by bringing in the Pd. In addition, in the plating solution using hydrazine as a reducing agent, if the plating object is immersed in the plating solution for a long time, only a small amount of the active ingredient in the plating solution is consumed. Nevertheless, there is a disadvantage that the deposition rate is significantly reduced. In addition, because the stability of the plating solution is poor, it is necessary to increase the concentration of ammonia, which is a complexing agent, which is not favorable in the working environment.In addition, divalent palladium salts and ethylenediamine An electroless palladium plating solution comprising methanetetraacetate, ethylenediamine, and sodium hypophosphite is also known (Japanese Patent Publication No. 46-26764), but this plating solution is known. However, they have poor stability and are decomposed in a short time.
更に、 上記したいずれのメ ツキ液でも、 得られるメ ッ キ皮膜は、 クラックが多く 、 ハンダ付け性が悪いことか ら、 電子部品へ適用することはできない。 また、 メ ツキ 皮膜を厚付けするとメ ツキ速度が著る しく遅く なるとと もに、 メ ツキ皮膜が黒色化して外観が悪く なるという欠 点ちめる 0
したがって現在までに報告されている無電解パラジゥ ムメ ツキ液は未だ実験室的規模を脱していない状況と言 る。 Furthermore, any of the above-mentioned plating liquids cannot be applied to electronic components because the resulting plating film has many cracks and poor solderability. In addition, when the plating film is thickened, the plating speed becomes extremely slow, and the plating film becomes black and the appearance becomes poor. Therefore, the electroless palladium plating solution that has been reported to date has not yet reached the laboratory scale.
—方、 ニッケルとパラジウムとを合金化させた P d— N i合金皮膜は、 有機性ガス雰囲気中においても、 有機 性ガスの存在に起因する弊害、 例えば、 有機性ガスのポ リマー化による接点部分の接触障害の発生等が少ないも のであることが知られている。 このため、 P d— N i合 金メ ッキの実用化が望まれているが、 工業的に実用化し 得る無電解 P d - N i合金メ ツキ液についての報告はほ とんどなされていない。 On the other hand, a Pd—Ni alloy film formed by alloying nickel and palladium can cause adverse effects due to the presence of an organic gas even in an organic gas atmosphere. It is known that there is little occurrence of contact failures in parts. For this reason, there is a demand for the practical use of Pd—Ni alloy metal plating. However, there have been few reports on electroless Pd—Ni alloy plating solutions that can be industrially commercialized. Absent.
例えば、 公知の無電解 P d— N i合金メ ッキ液と して は、 硫酸ニッケル 0. 1 1モル 、 塩化パラジゥム 〇 . 0 1 1モル 3 、 38%塩酸4 ^ 2 、 2 5 %アン モニァ水 1 60 mQ/ S 、 次亜リ ン酸ナ ト リ ウム For example, a known electroless Pd—Ni alloy plating solution includes nickel sulfate 0.11 mol, palladium chloride 0.11 mol 3, 38% hydrochloric acid 4 ^ 2, 25% ammonium chloride. Monitor water 1 60 mQ / S, sodium hypophosphite
0. ◦ 94モル からなる無電解 P d - N i 合金メ ッ キ液 (Electrocheni. Technology , 6_, 42 7 , ( 1 9 68) ) があるが、 このメ ツキ液は極めて安定性が悪く メ ツキ処理途中にメ ツキ液中での金属の急激な析出現象 所謂メ ツキ液の分解がおこ り、 それ故実用には不適当で ある。 There is an electroless Pd-Ni alloy plating solution consisting of 94 mol (Electrocheni. Technology, 6_, 427, (1968)), but this plating solution has extremely poor stability. During the plating process, a rapid precipitation phenomenon of the metal in the plating solution, that is, the decomposition of the plating solution occurs, which is unsuitable for practical use.
発明の開示
本発明の目的は、 工業規模においても実用可能なパラ ジゥム系無電解メ ツキ液を提供することにある。 Disclosure of the invention An object of the present invention is to provide a palladium-based electroless plating solution that can be used on an industrial scale.
本発明の他の目的は、 安定性に優れ、 かつ析出皮膜の 外観が良好なパラジゥム系無電解メ ツキ液を提供するこ とにある。 Another object of the present invention is to provide a palladium-based electroless plating solution having excellent stability and good appearance of a deposited film.
本発明の更に他の目的は、 析出皮膜の有孔度が小さ く 、 耐食性、 素地に対する密着性等の良好なパラジウム系無 電解メ ツキ液を提供することにある。 Still another object of the present invention is to provide a palladium electroless plating solution having a low porosity of a deposited film, good corrosion resistance, good adhesion to a substrate, and the like.
本発明の更に他の目的は、 作業性が良く 、 液管理の容 易なパラジゥム系無電解メ ツキ液を提供することにある。 Still another object of the present invention is to provide a palladium-based electroless plating solution having good workability and easy liquid management.
本発明の更に他の目的は、 クラックが少なく 、 ハンダ 付け性の良好なメ ツキ皮膜を形成し得るパラジゥム系無 電解メ ツキ液を提供することにある。 Still another object of the present invention is to provide a palladium-based electroless plating solution capable of forming a plating film with few cracks and good solderability.
本発明の更に他の目的は、 有機性ガス雰囲気中におい ても析出皮膜の表面特性の低下の少ない P d— N i合金 メ ツキ皮膜を形成し得るパラジゥム系無電解メ ツキ液を 提供することにある。 Still another object of the present invention is to provide a palladium-based electroless plating solution capable of forming a Pd—Ni alloy plating film with little decrease in the surface properties of a deposited film even in an organic gas atmosphere. It is in.
本発明の他の特徵は、 以下の記載から明確になるであ ろう。 Other features of the present invention will become clear from the following description.
本発明は、 以下に示すパラジウム系無電解メ ツキ液を 提供するものである。 The present invention provides the following palladium electroless plating solution.
① a ) ノヽ。ラ ジウム化合物 0 . 0 0 0 1 〜 0 . 5モル
b ) ア ンモニア及びア ミ ン化合物の少なく とも 1種① a) No. Radium compound 0.001 to 0.5 mol b) At least one of ammonia and amine compounds
〇. 00 1〜8モルノ8 〇. 00 1-8 Morno 8
c ) 二価の硫黄を含有する有機化合物 1〜 500 rag/ c) Organic compounds containing divalent sulfur 1 to 500 rag /
S 、 並びに S, and
d ) 次亜リ ン酸化合物及び水素化ホウ素化合物の少な く とも 1種 0. 005〜 1モル Z δ d) at least one of a hypophosphorous acid compound and a borohydride compound 0.005 to 1 mol Z δ
を含む水溶液からなることを特徵とするパラジゥム系 無電解メ ツキ液。 A palladium-based electroless plating solution characterized by being composed of an aqueous solution containing.
② a ) パラ ジウム化合物 0. 000 1〜 0. 5モル 2 b ) ニッケル化合物 0. 00 1〜 1モル/2 ② a) Palladium compound 0.001 to 0.5 mol 2 b) Nickel compound 0.001 to 1 mol / 2
c ) ア ンモニア及びア ミ ン化合物の少なく とも 1種 c) At least one of ammonia and amine compounds
0. 00 1〜 8モル/ S 0.00 1-8mol / S
d ) 二価の硫黄を含有する有機化合物 1〜 500 ingZ S 、 並びに d) organic compounds containing divalent sulfur from 1 to 500 ingZ S, and
e ) 次亜リ ン酸化合物及び水素化ホウ素化合物の少な く とも 1種 0. 005〜 1モル 2 e) at least one of a hypophosphorous acid compound and a borohydride compound 0.005 to 1 mol 2
を含む水溶液からなることを特徵とするパラジゥム系 無電解メ ツキ液。 A palladium-based electroless plating solution characterized by being composed of an aqueous solution containing.
本発明パラ ジウム系無電解メ ツキ液は、 ア ンモニア及 びア ミ ン化合物の少なく とも 1種と、 二価の硫黄を含有 する有機化合物とを安定剤と して併用するという全く新 規なものである。
この様なパラ ジウム系無電解メ ツキ液は、 極めて安定 性に優れたものであり、 外観、 物性ともに良好なパラジ ゥム系メ ツキ皮膜を形成することができる。 特に、 上記 安定剤を用い、 かつ金属源と して、 パラジウム化合物及 びニッケル化合物の両者を含有する無電解メ ツキ液は、 良好な外観及び物性を有する P d— N i合金メ ツキ皮膜 を形成することができ、 かつ安定性の良好な無電解メ ッ キ液である。 The palladium-based electroless plating solution of the present invention is a completely new method in which at least one of ammonia and an amine compound and an organic compound containing divalent sulfur are used in combination as a stabilizer. Things. Such a palladium-based electroless plating solution is extremely excellent in stability, and can form a palladium-based plating film having good appearance and physical properties. In particular, an electroless plating solution containing both a palladium compound and a nickel compound as a metal source using the above-described stabilizer and a Pd-Ni alloy plating film having good appearance and physical properties. It is an electroless plating solution that can be formed and has good stability.
本発明パラジウム系無電解メ ツキ液では、 P dの供給 源として塩化パラジゥム、 塩化パラジゥムナ ト リ ウム、 塩化パラジゥ厶カ リ ウム、 塩化パラ ジゥムア ンモニゥム, 硫酸パラジウム、 硝酸パラ ジウム、 酢酸パラジウム、 酸 化パラジゥム等のパラジゥム化合物を用いる。 パラジゥ ム化合物の濃度は 0. 0001〜 0. 5モル 2程度と し、 好ま し く は 0. 001〜0. 1モル 程度とする, 0. ◦ 0◦ 1モル を下回る濃度では、 メ ツキ皮膜の 折出速度が遅く なるので実用的ではなく 、 一方 0. 5モ ル を上回る濃度では、 析出速度がより向上すること はなく 、 更にメ ツキ液の安定性を阻害することになるの で好ま しく ない。 In the palladium electroless plating solution of the present invention, palladium chloride, palladium sodium chloride, palladium chloride, palladium ammonium chloride, palladium sulfate, palladium nitrate, palladium acetate, palladium acetate are used as the Pd supply source. A palladium compound such as palladium is used. The concentration of the palladium compound should be about 0.0001 to 0.5 mol 2, preferably about 0.001 to 0.1 mol. However, it is not practical because the deposition rate becomes slower. On the other hand, when the concentration exceeds 0.5 mol, the precipitation rate is not further improved and the stability of the plating solution is further impaired. Not good.
本発明メ ツキ液では、 液の安定性を維持するために、 ア ンモニア及びァ ミ ン化合物の少なく とも 1種と、 二価
の硫黄を含有する有機化合物とを組合せて用いることが 必要である。 ア ンモニア及びア ミ ン化合物はメ ツキ液中 の P dと錯体を形成してこれらの成分を液中に安定に保 持する作用をし、 液の安定化に寄与する。 ア ンモニア及 び 又はア ミ ン化合物の濃度は、 0 . 0 0 1 〜 8モル S 程度とし、 好ま しく は 0 . 0 1 〜 5モル 程度とす る。 ア ンモニアを単独で用いる場合には、 メ ツキ液の安 定性向上のために 0 . 0 7 5モル 程度以上とするこ とがより好ま しい。 アンモニア及び 又はア ミ ン化合物 の濃度が高いほど液の安定性は良好になるが、 上記範囲 を上回る濃度では、 不経済であり、 特にア ンモニアを用 いる場合には臭気等により作業環境が悪く なるので好ま しく ない。 また、 上記範囲を下回る濃度では液の安定性 が低下して、 メ ツキ液が分解し易く なるので好ま し く な い。 In the plating solution of the present invention, in order to maintain the stability of the solution, at least one of ammonia and an amide compound is added to the divalent solution. It is necessary to use in combination with a sulfur-containing organic compound. The ammonia and amine compounds form a complex with Pd in the plating solution to stably maintain these components in the solution and contribute to the stabilization of the solution. The concentration of the ammonia and / or the amine compound is about 0.001 to 8 mol S, preferably about 0.01 to 5 mol. When using ammonia alone, it is more preferable to use about 0.075 mol or more in order to improve the stability of the plating solution. The higher the concentration of ammonia and / or amine compound, the better the stability of the liquid.However, if the concentration exceeds the above range, it is uneconomical, especially when using ammonia, the working environment is poor due to odor etc. I don't like it. On the other hand, if the concentration is below the above range, the stability of the solution is reduced, and the plating solution is easily decomposed.
本発明では、 ァ ミ ン化合物とは、 ァ ミ ノ酸類も包含す る ものとする。 本発明での使用に適するァ ミ ン化合物と しては、 具体的にはモノア ミ ン類と して、 メ チルァ ミ ン、 ェチルァ ミ ン、 プロ ピルァ ミ ン、 ジメ チルァ ミ ン、 ト リ メ チルァ ミ ン、 ジメ チルェチルァ ミ ン、 ベンジルァ ミ ン、 2 —ナフチルァ ミ ン、 イ ソプチルァ ミ ン、 イ ソア ミ ノレァ ミ ン等、 ジァ ミ ン類と して、 メ チレ ンジァ ミ ン、 ェチレ
ンジァ ミ ン、 テ トラメチレンジァ ミ ン、 ペンタメチレン ジァ ミ ン、 へキサメチレンジァ ミ ン等、 ポリア ミ ン類と して、 ジエチレン ト リア ミ ン、 テ トラエチレンペンタ ミ ン、 ペンタエチレンへキサミ ン、 へキサエチレンヘプタ ミ ン等、 ア ミ ノ酸類と して、 エチレンジア ミ ン四酢酸又 はそのナ ト リ ウム塩、 N —ヒ ドロキシエチレンジァ ミ ン 三酢酸又はそのナ ト リ ウム塩、 グリ シン、 N —メチルダ リ シン、 ジメチルグリ シン、 イ ミ ノ ジ酢酸、 ヒダン トイ ン酸、 グリ コシァ ミ ン等、 イ ミ ダゾリ ン類として、 イ ミ ダ'ゾリ ン、 2—メチルー 2—イ ミ ダゾリ ン、 2 —フェ^ ノレ一 2—ィ ミ ダゾリ ン、 2—ベンジル一 2—ィ ミ ダゾリ ン、 1 , 2 —ジフエ二ルー 2 —イ ミ ダゾリ ン、 2 , 4 , 5 — ト リ フエ二ルー 2 —イ ミ ダゾリ ン、 2 , 2 ' — ビス ( 2—イ ミ ダゾリ ン） 、 2—クロルメチルー 2—イ ミ ダ ゾリ ン等を例示できる。 In the present invention, the amide compound also includes amic acids. Examples of the amide compounds suitable for use in the present invention include monoamines such as methylamine, ethylamine, propylamine, dimethylamine, and trimamine. Chilamin, dimethylethylamine, benzylamine, 2-naphthylamine, isoptilamine, isoaminoleamine, etc. Polyamines such as diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, etc. Amino acids such as oxaethyleneheptamine, ethylenediaminetetraacetic acid or its sodium salt, N-hydroxyethylenediaminetriacetic acid or its sodium salt, Imidazolin, 2-methyl-2-imid as imidazolines, such as syn, N-methyldaricin, dimethylglycine, iminodiacetic acid, hydantoic acid, and glycosamine. Dazolin, 2-Fe-N- 2-imidazolin, 2-Benzyl-2-imidazolin, 1,2-Diphen-2-ru 2-Imidazolin, 2,4,5-Triffe Lou 2 - Lee Mi Dazori emissions, 2, 2 '- bis (2-i Mi Dazori down), can be exemplified 2- Kurorumechiru 2 Lee Mi Da sledding down like.
本発明では、 アンモニア及びア ミ ン化合物の少なく と も 1種の化合物と しては、 好ま しく は、 アンモニア、 ジ ァ ミ ン類及びポリァ ミ ン類から選ばれたものを使用でき より好ま しく は、 アンモニア、 エチレンジァ ミ ン及びジ エチレン ト リア ミ ンから選ばれたものを使用できる。 In the present invention, as at least one compound of ammonia and an amine compound, one selected from ammonia, diamines and polyamines can be preferably used. Can be selected from ammonia, ethylenediamine and diethylenetriamine.
本発明では、 上記したァ ミ ン化合物及びァン乇ニァの 少なく とも 1種を使用すればよいが、 ア ンモニアを単独
で使用する場合には、 メ ツキの初期発生までの時間、 即 ち被メ ツキ物をメ ツキ液に浸漬した後、 メ ツキが付着し はじめるまでの時間が長く なることがある。 この様な場 合には、 ァ ンモニァと上記したァ ミ ン化合物とを併用す ることによって初期発生時間を短縮することができる。 In the present invention, at least one of the above-described amide compounds and pendants may be used, but ammonia alone is used. In the case of using it, the time until the initial generation of the plating, that is, the time until the plating starts to be adhered after the object to be plated is immediately immersed in the plating liquid may be increased. In such a case, the initial generation time can be reduced by using the ammonia and the above-mentioned amine compound in combination.
ァ ミ ン化合物量はァンモニァと併用する場合には When the amount of amide compound is used in combination with ammonia,
〇. 0 0 0 5モルノ S 程度以上で初期発生時間を短縮す る効果がある。 また、 ア ミ ン化合物を配合したメ ツキ液 では、 メ ツキ皮膜の厚付けを行なった場合のメ ツキ皮膜 の外観が特に良好になる。 〇. At about 0.05 molno S or more, there is an effect of shortening the initial generation time. In addition, in the case of a plating solution containing an amine compound, the appearance of the plating film becomes particularly good when the plating film is thickened.
本発明での使用に適する二価の硫黄を含有する有機化 合物と しては、 具体的には、 The divalent sulfur-containing organic compound suitable for use in the present invention includes, specifically,
(CH3 ) 3 CSH, CH3 (CH2 ) 6 CH (CH3 ) S H, (CH 3 ) 3 CSH, CH 3 (CH 2 ) 6 CH (CH 3 ) SH,
CH3 (CH2 ) 1 1 SH, HS CH2 COOH, HS CH2 C H2 COOH, CH 3 (CH 2 ) 1 1 SH, HS CH 2 COOH, HS CH 2 CH 2 COOH,
等のメ ルカ プタ ン類 H5 ) a S, (i s o-C3 H7 ) 2 S
CH- S -Cs H:
Mercaptans such as H 5 ) a S, (is oC 3 H 7 ) 2 S CH- S -Cs H:
HOOC CH2 S CH2 COOH, HOOC CH 2 S CH 2 COOH,
HOOC CH2 CH2 S CH2 CH2 COOH 等のスルフ ィ ド類 Sulfides such as HOOC CH 2 CH 2 S CH 2 CH 2 COOH
(CH3 ) 2 S2 , (C2 H5 ) 2 S2 , (C3 H7 ) 2 S (CH 3 ) 2 S 2 , (C 2 H 5 ) 2 S 2 , (C 3 H 7 ) 2 S
S S
s2 - c s 2 -c
等を例示でき、 これらのうちスルフイ ド類及びジスルフ ィ ド類が好ま しい。 これらの硫黄含有有機化合物は単独 又は適宜組み合わせて使用できる。 硫黄含有有機化合物 の使用量は、 1〜 500 mgZ S程度と し、 好ま しく は 5 〜 1 0 OfflgZG程度とする。 硫黄含有有機化合物の使用 量が上記範囲を上回ると、 メ ツキ皮膜の析出速度が低下 し、 また析出したメ ツキ皮膜の外観も劣化するので好ま
しく ない。 また上記範囲を下回る濃度では、 メ ツキ液の 安定性が不充分となるので不適当である。 And the like. Of these, sulfides and disulfides are preferred. These sulfur-containing organic compounds can be used alone or in appropriate combination. The amount of the sulfur-containing organic compound to be used is about 1 to 500 mgZS, preferably about 5 to 10 OfflgZG. When the use amount of the sulfur-containing organic compound exceeds the above range, the deposition rate of the plating film is reduced, and the appearance of the deposited plating film is also deteriorated. Not good. Concentrations below the above range are not suitable because the stability of the plating solution becomes insufficient.
本発明メ ツキ液は、 上記した様に、 ア ンモニア及び/ 又はア ミ ン化合物と硫黄含有有機化合物とを併用するこ とを必須とする ものであり、 極めて安定性に優れた工業 的規模での使用に好適なメ ツキ液である。 As described above, the plating solution of the present invention requires the use of ammonia and / or an amine compound and a sulfur-containing organic compound in an essential manner, and is extremely stable on an industrial scale. It is a plating solution suitable for use.
本発明メ ツキ液では、 金属イオンを還元するための還 元剤と して、 次亜リ ン酸化合物及び水素化ホウ素化合物 の少なく とも 1種を使用する。 次亜リ ン酸化合物と して は、 次亜リ ン酸又はそのァンモニゥム、 リ チウム、 ナ ト リ ウム、 カ リ ウム、 カルシウム塩等を使用でき、 水素化 ホウ素化合物と してはジメ チルァ ミ ンボラ ン、 ト リ メ チ ルァ ミ ンボラ ン、 イ ソプロ ピルア ミ ンボラ ン、 モルホ リ ンボラン等のア ミ ンボラ ン類や水素化ホウ素ナ ト リ ウム、 水素化ホウ素カ リ ウム等を使用できる。 還元剤の使用量 は、 0 . 0 0 5〜 1モル ^ 程度と し、 好ま しく は 〇 . 0 1 〜 0 . 5モル 程度とする。 使用量が In the plating solution of the present invention, at least one of a hypophosphorous acid compound and a borohydride compound is used as a reducing agent for reducing metal ions. As the hypophosphorous acid compound, hypophosphorous acid or its ammonium, lithium, sodium, potassium, calcium salt and the like can be used, and as the borohydride compound, dimethylethyl is used. Aminboranes such as uranium, trimethylamine, isopropylamine, morpholine borane and the like, sodium borohydride, potassium borohydride and the like can be used. The amount of the reducing agent used is about 0.05 to 1 mol ^, preferably about 0.1 to 0.5 mol. Consumption
0 . 0 0 5モル Z S 未満ではメ ツキが充分に析出せず、 —方 1モル を上回るとメ ツキ液が不安定になるので 好ま しく く ない。 If the amount is less than 0.05 mol ZS, the plating is not sufficiently precipitated, and if it exceeds 1 mol, the plating solution becomes unstable, which is not preferable.
本発明メ ツキ液は、 前記した様に、 ア ンモニアと特定 の硫黄含有有機化合物とを組み合わせて用いることによ
る極めて安定性に優れたものであり、 それ故上記した様 に各種の還元剤を使用できる。 As described above, the plating solution of the present invention is obtained by using ammonia in combination with a specific sulfur-containing organic compound. It is extremely excellent in stability, and therefore various reducing agents can be used as described above.
本発明パラジウム系無電解メ ツキ液は、 上述した有効 成分である a ) パラジウム化合物、 b ) アンモニア及び ァ ミ ン化合物の少なく とも 1種、 c ) 二価の硫黄を含有 する有機化合物、 並びに d ) 次亜リ ン酸化合物及び水素 化ホウ素化合物の少なく とも 1種、 The palladium-based electroless plating solution of the present invention comprises: a) a palladium compound, b) at least one of ammonia and an amine compound, c) an organic compound containing divalent sulfur, and d) ) At least one of a hypophosphorous acid compound and a borohydride compound;
を水に溶解して水溶液と したものであって （以下、 P d メ ツキ液という） 、 液の安定性が良好であり、 外観、 物 性ともに優れた P dメ ツキ皮膜を形成することができる。 Is dissolved in water to form an aqueous solution (hereinafter referred to as a Pd plating solution), which has good liquid stability and can form a Pd plating film with excellent appearance and physical properties. it can.
また、 本発明では、 このメ ツキ液に、 更に、 ニッケル 化合物を添加することによって、 パラジウム一ニッケル 合金メ ツキ皮膜を形成し得るパラジゥム系無電解メ ツキ 液 （以下、 P d— N i メ ツキ液という） を得ることがで きる。 この様なニッケル化合物を添加した無電解メ ツキ 液 （ P d— N i メ ツキ液） は、 上記した P dメ ツキ液と 同様に優れた安定性を有するものであり、 また形成され る P d— N i 合金メ ッキ皮膜は、 P dメ ツキ液によって 得られる P d単独のメ ツキ皮膜と同様の優れた外観及び 物性を有する ものである。 Further, in the present invention, a palladium-based electroless plating solution (hereinafter referred to as a Pd-Ni plating solution) capable of forming a palladium-nickel alloy plating film by further adding a nickel compound to the plating solution. Liquid) can be obtained. The electroless plating solution (Pd—Ni plating solution) to which such a nickel compound is added has the same excellent stability as the above-mentioned Pd plating solution, and the P The d—Ni alloy plating film has the same excellent appearance and physical properties as the plating film of Pd alone obtained by the Pd plating solution.
本発明 P d— N i メ ツキ液における使用に適するニッ ゲル化合物と しては、 塩化ニッケル、 塩化ニッケルアン
モニゥム、 臭化ニッケル、 ヨウ化ニッケル、 硫酸ニッケ ル、 硫酸ニッケルア ンモニゥム、 硝酸ニッケル、 炭酸二 ッゲル、 スルフア ミ ン酸ニッケル、 酢酸ニッケル、 安息 香酸ニッケル、 クェン酸ニッケル、 ギ酸ニッケル、 酒石 酸ニッケル、 しゅう酸ニッケル等を例示できる。 ニッケ ル化合物の濃度は、 0 . 0 0 1 〜 1 モル/ S 程度と し、 好ま しく は 0 . 0 1 〜 0 . 5モル 程度とする。 Nickel compounds suitable for use in the Pd—Ni plating solution of the present invention include nickel chloride and nickel chloride. Monium, Nickel bromide, Nickel iodide, Nickel sulfate, Nickel sulfate ammonium, Nickel nitrate, Nigel carbonate, Nickel sulfamate, Nickel acetate, Nickel benzoate, Nickel citrate, Nickel formate, Nickel tartrate And nickel oxalate. The concentration of the nickel compound is about 0.01 to 1 mol / S, and preferably about 0.01 to 0.5 mol.
〇 . 0 0 1モル Z 2 未満では、 ニッケルが析出し難く 、 —方 1 モルノ S を上回る濃度では、 メ ツキ液の安定性が 低下し、 また、 ニッケル化合物の溶解のためにアンモニ ァ及び/ /又はア ミ ン化合物を多量に添加することが必要 となり、 不経済である。 特に、 ア ンモニアを使用する場 合には、 臭気等によって作業環境が悪く なるので好ま し く ない。 If the concentration is less than 0.01 mol Z 2, nickel is difficult to precipitate, whereas if the concentration is higher than 1 molno S, the stability of the plating solution is reduced, and ammonia and / or It is necessary to add a large amount of an amine compound, which is uneconomical. In particular, when ammonia is used, it is not preferable because the working environment is deteriorated due to odor and the like.
P d— N i メ ツキ液において、 ニッケル化合物以外の 成分については、 使用化合物の種類及び使用量ともに前 記した P dメ ツキ液と同様でよい。 In the Pd-Ni plating solution, components other than the nickel compound may be the same as the Pd plating solution in terms of the type and amount of the compound used.
P d - N i メ ツキ液から析出する P d— N i 合金メ ッ キ皮膜中のパラジウムとニッケルの比率は、 P d— N i メ ツキ液中のパラジウム化合物とニッケル化合物との濃 度比を変化させることによって調整でき、 任意の組成の メ ツキ皮膜を容易に得ることができる。
本発明のパラジウム系無電解メ ツキ液は、 以上示した 各有効成分を水に溶解して水溶液とすることによって得 られるものである。 該メ ツキ液では、 p H調整を行なう ことは必須ではないが、 P dメ ツキ液では、 11を 5〜 1 0程度に調整することが好ま しく 、 また、 P d— N i メ ツキ液では、 p Hを 5〜 1 1程度に調整することが好 ま しい。 この様な p H調整を行なったメ ツキ液を用いる 場合には、 クラックのほとんどないメ ツキ皮膜を形成す ることが可能となる。 得られたクラックのほとんどない メ ツキ皮膜は、 ハングのぬれ性が良く 、 ハンダ付け性が 良好である。 メ ツキ液の p H調整は、 冽えば H C S 、 H 2 S 0 4 等の酸や N a 0 H等アルカ リ化合物によって 行なえばよい。 The ratio of palladium to nickel in the Pd—Ni alloy plating film deposited from the Pd-Ni plating solution is determined by the concentration ratio of the palladium compound to the nickel compound in the Pd—Ni plating solution. Can be adjusted by changing the thickness of the film, and a paint film having an arbitrary composition can be easily obtained. The palladium electroless plating solution of the present invention is obtained by dissolving each of the active ingredients described above in water to form an aqueous solution. In the plating solution, it is not essential to adjust the pH, but in the case of the Pd plating solution, it is preferable to adjust 11 to about 5 to 10 and the Pd—Ni plating solution. Then, it is preferable to adjust the pH to about 5 to 11. In the case of using a plating solution having such pH adjusted, a plating film having almost no cracks can be formed. The resulting paint film with almost no cracks has good hang wettability and good solderability. P H adjustment of main luck solution may be performed by Kiyoshie if HCS, H 2 S 0 acid and N a 0 H such alkali compounds such as 4.
本発明メ ツキ液 （ P dメ ツキ液及び P d — N i メ ツキ 液） は、 1 0〜 9 0て程度という広い範囲の温度におい てメ ツキ可能であり、 特に 2 5〜 7 0 °C程度の液温のと きに、 平滑で光沢のある最も良好なメ ツキ皮膜が得られ る。 この様に比較的低温においても、 メ ツキを行ない得 ることから、 メ ツキ液の管理が容易となり、 特にアンモ ニァを用いる場合には、 アンモニアの揮発を抑えること が可能となって、 作業環境を良好に保つことができる。 また、 本発明メ ツキ液では、 液温が高い程、 メ ツキ皮膜
の析出速度が速く なる傾向があり、 上記した温度範囲内 で適宜温度を設定することにより任意の析出速度とする ことができる。 The plating solution of the present invention (Pd plating solution and Pd—Ni plating solution) can be plated at a wide temperature range of about 10 to 90, and particularly 25 to 70 °. At a liquid temperature of about C, a smooth and glossy best paint film can be obtained. As described above, the plating can be performed even at a relatively low temperature, so that the control of the plating solution can be easily performed. In particular, when ammonia is used, the volatilization of ammonia can be suppressed. Can be kept good. In the plating liquid of the present invention, the higher the liquid temperature, the more the plating film There is a tendency for the precipitation rate to increase, and an arbitrary deposition rate can be obtained by appropriately setting the temperature within the above-mentioned temperature range.
本発明メ ツキ液では、 メ ツキ'皮膜の析出速度は、 液温 の他に、 金属分の濃度にも依存するが、 その他の成分の 濃度ゃメ ツキ液の p Hの変動にはほとんど影響を受けな い。 このため、 本発明メ ツキ液では、 金属分濃度、 及び メ ツキ液の液温を調整することによって、 メ ツキ皮膜の 膜厚のコ ン トロールを容易に行なう ことができる。 In the plating solution of the present invention, the deposition rate of the plating film depends not only on the temperature of the solution but also on the concentration of the metal component, but it has almost no effect on the fluctuation of the concentration of other components divided by the pH of the plating solution. Do not receive. Therefore, in the plating solution of the present invention, the thickness of the plating film can be easily controlled by adjusting the concentration of the metal component and the temperature of the plating solution.
本発明メ ツキ液により メ ツキ処理を行なうには、 前記 した温度範囲内のメ ツキ液中に、 ？ 01皮膜又は？ （3 — In order to perform the plating process with the plating solution of the present invention, it is necessary to include? 01 film or? (3 —
N i 皮膜の還元析出に対して触媒性のある基質を浸潰す ればよい。 触媒性のある基質と しては、 例えば、 F e、 C o、 N i C u、 S n、 A g、 A u、 P t、 P d及び これらの合金等を示すことができる。 また、 樹脂、 ガラ ス、 セラ ミ ックス、 W等の触媒性のない基質であっても、 例えば、 センシタイ ジングーアクチベータ法、 キヤタ リ ス トーァクセラ レーター法等の公知の方法で触媒性を付 与することによって、 上記方法と同様にメ ツキ液中に浸 漬してメ ツキ処理を行なう ことができる。 What is necessary is just to immerse the substrate which has a catalytic property for the reductive deposition of the Ni film. Examples of the catalytic substrate include Fe, Co, NiCu, Sn, Ag, Au, Pt, Pd, and alloys thereof. Even non-catalytic substrates such as resin, glass, ceramics, and W can be provided with a catalytic property by a known method such as, for example, a sensitizing activator method or a catalytic catalyzer method. Thus, the plating process can be performed by immersion in the plating solution as in the above method.
本発明メ ツキ液によるパラジウム皮膜又はパラジウム ♦ ニッケル合金皮膜の析出は、 自己触媒的に進行し、 こ
のため有孔度が小さ く 、 しかも密着性の高い皮膜が得ら れる。 The deposition of the palladium film or the palladium nickel alloy film by the plating solution of the present invention proceeds autocatalytically. Therefore, a film having low porosity and high adhesion can be obtained.
本発明無電解パラジウムメ ツキ液は、 以下の様な優れ た特性を有する。 The electroless palladium plating liquid of the present invention has the following excellent properties.
① 極めて安定性に優れたメ ツキ液である。 ① Extremely stable plating solution.
② 得られるメ ツキ皮膜の外観が良好であり、 膜厚を厚 く した場合にも良好な外観のメ ツキ皮膜となる。 (2) The appearance of the obtained plating film is good, and even when the film thickness is increased, the plating film has a good appearance.
③ 自己触媒性の析出であることから析出皮膜の有孔度 が小さく 、 耐食性が良好であり、 また、 素地に対する 密着性が良い。 ③ Because of autocatalytic deposition, the porosity of the deposited film is small, the corrosion resistance is good, and the adhesion to the substrate is good.
④ メ ツキ液の安定性が良いので、 低ア ンモニア量で使 用でき、 ア ンモニアの揮発を抑制することができる。 またア ミ ン化合物を使用するメ ツキ液では、 メ ツキ作 業中や保存中にァ ミ ン化合物が揮発することはない。 このため、 メ ツキ液の保存安定性が良く 、 また作業環 境も良好である。 の The stability of the plating solution is good, so it can be used with a low amount of ammonia and can suppress the volatilization of ammonia. In addition, in a plating solution using an amine compound, the amine compound does not volatilize during the plating operation or during storage. Therefore, the storage stability of the plating solution is good, and the working environment is also good.
⑤ 低温で析出可能であるため、 作業性が良く 、 また、 アンモニア浴と して用いる場合にも、 ア ンモニアの揮 発が少く 、 メ ツキ液の管理が容易である。 (4) Since precipitation can be performed at a low temperature, workability is good, and even when used as an ammonia bath, there is little volatilization of ammonia and the control of the plating solution is easy.
⑥ 析出速度は、 金属濃度と液温にのみ依存し、 他の成 分の濃度や液の p Hには、 ほとんど影響されないので、 メ ツキ膜厚のコン トロールが容易である。
⑦ p Hを中性付近に設定することにより、 使用できる 被処理物、 レジス トイ ンキ等の種類が多く なり、 また メ ツキ設備の材質と しても多種類のものが使用できる。(4) The deposition rate depends only on the metal concentration and the solution temperature, and is hardly affected by the concentration of other components or the pH of the solution, so that control of the plating film thickness is easy. こ と By setting the pH to near neutrality, the types of objects to be treated, resist tongues, etc. that can be used are increased, and various types of plating equipment can be used.
⑧ P dメ ツキ液では p Hを 5〜 1 0に調整することに よって、 また P d— N i メ ツキ液では p Hを 5〜： L 1 に調整することによってクラックの非常に少ないメ ッ キ皮膜が得られる。 この様なメ ツキ皮膜はハンダ付け 性が良好であり、 電子部品への応用に適する ものであ る 0 メ By adjusting the pH to 5 to 10 for the Pd plating solution, and by adjusting the pH to 5 to L1 for the Pd—Ni A sticky film is obtained. Such a plating film has good solderability and is suitable for application to electronic components.
⑨ P d— N i メ ツキ液では、 液中の P d と N i の比を 変化させることにより、 用途に応じた任意の組成の P d — N i 合金メ ッキが容易に得られる。 また、 得ら れる P d - N i合金皮膜は、 有機性ガス雰囲気中でも 析出皮膜の表面にポリマーを生じることがなく 、 信頼 性の要求される電気接点部品への応用に最適である。 本発明メ ツキ浴は、 上記した様に優れた特性を有する パラジゥム系無電解メ ツキ液であり、 電子部品において 高い ί言頼性が要求される接点部品への応用や金メ ッキ皮 膜の長寿命化のための下地メ ツキ皮膜と しての応用等に 極めて有用であり、 更に、 その他、 特に耐食性が要求さ れる部品等に対して広く使用し得る ものである。 で は In the Pd—Ni plating solution, by changing the ratio of Pd to Ni in the solution, a Pd—Ni alloy plating of any composition according to the application can be easily obtained. Further, the obtained Pd-Ni alloy film does not generate a polymer on the surface of the deposited film even in an organic gas atmosphere, and is most suitable for application to electrical contact parts requiring high reliability. The plating bath of the present invention is a palladium-based electroless plating solution having excellent characteristics as described above, and is applied to contact parts requiring high reliability in electronic parts, and to a gold plating film. It is extremely useful for application as a base plating film for prolonging the service life, and can be widely used for other parts, especially those requiring corrosion resistance.
図面の簡単な説明
第 1図は、 P dメ ツキ液におけるメ ツキ時間と析出し たメ ツキ皮膜の膜厚との関係を示すグラフ、 第 2図は、 P d - N i メ ツキ液中の N i と P dの比と析出物中の N i量との関係を示すグラフ、 第 3図は P d— N i メ ッ キ液におけるメ ツキ時間と析出量との関係を示すグラフ、 第 4図は P d— N i メ ツキ液における液温と析出速度の 関係を示すグラフ、 第 5図は P d - N i メ ツキ液におけ る液温と析出物中の N i量との関係を示すグラフである。 BRIEF DESCRIPTION OF THE FIGURES Fig. 1 is a graph showing the relationship between plating time and the thickness of the deposited plating film in the Pd plating solution, and Fig. 2 is a graph showing Ni and P in the Pd-Ni plating solution. Fig. 3 is a graph showing the relationship between the ratio of d and the amount of Ni in the precipitate, Fig. 3 is a graph showing the relationship between plating time and the amount of precipitation in the Pd-Ni plating solution, and Fig. 4 is P Fig. 5 is a graph showing the relationship between the liquid temperature and the deposition rate in the d-Ni plating solution. Fig. 5 is a graph showing the relationship between the liquid temperature in the Pd-Ni plating solution and the amount of Ni in the precipitate. It is.
発明を実施するための最良の形態 BEST MODE FOR CARRYING OUT THE INVENTION
以下実施例を示して本発明を更に詳細に示す。 Hereinafter, the present invention will be described in more detail with reference to Examples.
実施例 1 Example 1
下記組成メ ツキ液を調製した。 The following composition plating solution was prepared.
o P d C δ 2 〇 . 0 1モル/ 2 o P d C δ 2 〇. 0 1 mol / 2
οァ ンモニァ （ 28%) 2 0 0 ΙΠβ / δ ο Ammonia (28%) 2 0 0 ΙΠβ / δ
( 3. 0モル/ S ) (3.0 mol / S)
οエチレ ンジア ミ ン ο Ethylene Min
四酢酸ナ ト リ ウム Sodium tetraacetate
( E D T A ♦ 2 N a ) 0. 0 1モル S (E D T A ♦ 2 N a) 0.0 1 mol S
oチォジグリ コール酸 2 0 fflg/ δ o Thiodiglycolic acid 20 fflg / δ
o N a Η2 Ρ 02 0. 08モル/ S o N a Η 2 Ρ 0 2 0.08 mol / S
上記メ ツキ液を用いて液温 3 CTCと 4 0ての 2通りで 銅板にメ ツキを行なった。 メ ツキ膜厚とメ ツキ時間との
関係のグラフを第 1図に示す。 Using the above plating solution, plating was performed on the copper plate at two temperatures, 3 CTC and 40. The relationship between plating film thickness and plating time A graph of the relationship is shown in FIG.
第 1図から判る様に、 析出速度は、 液温 3 0 eCで As it can be seen from Figure 1, deposition rate, at a liquid temperature 3 0 e C
1 . 0 m Z時間、 4 0 。Cで 1 . 3 m Z時間であり、 時間と共にメ ツキ膜厚は直線的に増加した。 この事から、 メ ツキ皮膜の析出が自己触媒的に進行し、 しかも析出速 度の安定性が極めて良好であることが判る。 1.0 mZ hours, 40. The time was 1.3 mZ for C, and the plating film thickness increased linearly with time. From this, it can be seen that the deposition of the plating film proceeds autocatalytically, and the stability of the deposition rate is extremely good.
得られたメ ツキ皮膜の折曲げテス トを行なった結果、 密着性は極めて良好であった。 また、 6時間メ ツキを行 ない、 厚付け皮膜を形成させた場合にも、 光沢銀白色の 良好な外観の皮膜が得られた。 The obtained paint film was subjected to a bending test, and as a result, the adhesion was extremely good. In addition, when a thick coating film was formed by performing the plating for 6 hours, a glossy silver-white film having a good appearance was obtained.
また、 上記メ ツキ液の安定性を調べるために、 9 〇て への加熱、 2 5。Cでの密閉保存、 及び 2 5。Cでの開放保 存を行なった結果を第 1表に示す。 尚、 比較と して、 下 記組成の従来浴についても同様に安定性試験を行なった。 o従来浴① In addition, heating to 9 安定 to check the stability of the above plating solution, 25. Store tightly closed in C, and 25. Table 1 shows the results of open storage at C. For comparison, a stability test was similarly performed on a conventional bath having the following composition. o Conventional bath
P d C δ 2 5 . 4 g δ P d C δ 25.4 g δ
アンモニア 3 5 0 g δ Ammonia 350 g δ
E D T A ♦ 2 N a 3 4 g Q E D T A ♦ 2 N a 3 4 g Q
ヒ ドラ ジ ン 0 . 3 g Q Hydrazin 0.3 g Q
o従来浴② o Conventional bath
P d C 2 ？ 1 〇 . 0 g / δ P d C 2? 1 〇 .0 g / δ
E D T A ♦ 2 N a 9 . 0 g / δ
エチレンジア ミ ン 2 5. 6 g / 2 EDTA ♦ 2 Na 9.0 .0 g / δ Ethylene diamine 25.6 g / 2
N a H2 P 0 a 4 g / Q N a H 2 P 0 a 4 g / Q
1 1
9〇 への 25 C密閉 25°C開放 加熱 保存 保存 本発明メツキ液 分解せず 4力月保存 7日で分解 後分解なし 25 ° C closed to 25〇 Open at 25 ° C Heat Storage Preservation Storage solution of the present invention No decomposition
従来浴① 5分以内に 1週間で 1日以内に 分解 分解 分解 従来浴② 5分以内に 2週間で 1日以内に 分解 分解 分解
Conventional bath① Decomposes within 1 minute within 1 week within 5 minutes Conventional bath 分解 Decomposes within 1 day within 2 minutes within 5 minutes
以上の結果から、 本発明メ ツキ液の安定性は、 極めて 優れたものであることが判る。 From the above results, it can be seen that the stability of the plating solution of the present invention is extremely excellent.
実施例 2 Example 2
実施例 1 に示す本発明メ ツキ液を下記第 2表に示す各 ρ Η値に調製し （H C S 使用） 、 液温 4 0 °Cで銅板上に 1 m厚にメ ツキ皮膜を形成させた。 尚、 無調整のメ ッ キ液は p H 1 1 . 5であった。 得られたメ ツキ皮膜の状 態を走査型電子顕微鏡 （ 3 0 0 0倍） で観察した後、 下 記の方法でハ ンダ付け性試験を行なった。 結果を第 2表 に示す。 The plating solution of the present invention shown in Example 1 was prepared to each ρΗ value shown in Table 2 below (using HCS), and a plating film having a thickness of 1 m was formed on a copper plate at a liquid temperature of 40 ° C. . The unadjusted paint solution had a pH of 11.5. After observing the state of the obtained paint film with a scanning electron microscope (3000 magnification), a solderability test was performed by the following method. Table 2 shows the results.
o ハンダ付け性試験 o Solderability test
メ ツキ皮膜を形成させた試料 （ 2 5 m in x 2 5 m m X Sample with a plating film (25 m in x 25 mm x
0 . 3 mi) をロジ ンフラックス （ロジ ン 2 5 %イ ソプロ ピルアルコール溶液） に浸漬して前処理した後、 メニス コ グラフ （フイ リ ップス社製） を使用し、 2 3 0。Cで溶 融させた 6 4ハング （スズ ： 鉛 = 6 ： 4 ) 中に試料を ハンダ面に垂直に 1 2 fflmの深さまで浸漬し、 ハンダと試 料面との接触角が 9 0度になるまでの時間を測定してゼ 口 ク ロスタイムと した （M I L L S T D— 8 8 3 B に 準ずる） 。 ゼロク ロスタイムが短い程メ ツキ皮膜に対す るハングのぬれ性が良好であるといえる。 次いで、 ゼロ ク ロスタイムを測定した後の試料について、 付着したハ
ンダの状態を観察し、 ハングの付着性を調べた。 結果を 次の記号で示す。 0.3 mi) was immersed in a rosin flux (25% rosin isopropyl alcohol solution) for pretreatment, and then used with a meniscograf (manufactured by Phillips). The sample was immersed vertically into the solder surface to a depth of 12 fflm in a 64 hang (tin: lead = 6: 4) melted with C, and the contact angle between the solder and the sample surface was reduced to 90 degrees. The time required to reach this point was measured and defined as the mouth cross time (according to MILLSTD—8883B). It can be said that the shorter the zero cross time, the better the wettability of the hang on the paint film. Next, for the sample after measuring the zero cross time, The condition of the hanger was observed and the adhesion of the hang was examined. The results are indicated by the following symbols.
A…ハンダが均一に付着 A: Solder adheres uniformly
B——部不均一である 浸漬面の 9 8 %以上にハンダが 付着 B ---- Part is not uniform.
C ンダの付着面が 9 8 %未満であり、 付着状態が不 均一である。 第 2 表 ハンダ付け性 The adhered surface of carbon is less than 98%, and the adhered state is not uniform. Table 2 Solderability
p H メツキ^ ^の ゼロクロ ンタ、 '付け メツキ速度 髓 スタイム 後の外観 mZ時間） pH counter ^ ^, zero clock, 、 付 け メ 速度 外 観 外 観 外 観 外 観
1 1. 5 クラック有り 5秒以上 C 1. 3 本 1 0 微小なクラッ 4. 2秒' B 1. 2 ク有り 1 1.5 cracks 5 seconds or more C 1.3 3 10 minute cracks 4.2 seconds' B 1.2 cracks
明 9 クラック無し 3. ◦秒 A 1. 2 浴 8 2. 8秒 A 1. 2 Light 9 No crack 3.Sec.A1.2 Bath 82.8S A1.2
7 // 2. 9秒 A 1. 1 餘浴① クラック有り 5秒以上 C 0. 5 魏浴② " C 0. 6
実施 3 7 // 2.9 seconds A 1.1 Bath ① cracks 5 seconds or more C 0.5 Wei bath ② C 0.6 Implementation 3
E D T A ♦ 2 N a量を下記第 3表に示す変量とする以 外は、 実施例 1 と同様のメ ツキ浴を使用して、 銅板上に メ ツキを行ない、 銅板をメ ツキ液中に浸漬した後、 ノ、。ラ ジゥムの析出が始まるまでの時間、 即ち初期発生時間を 求めた。 結果を第 3表に示す。 Using the same plating bath as in Example 1, plating was performed on the copper plate, and the copper plate was immersed in the plating solution, except that the EDTA ♦ 2 Na amount was changed to the variable shown in Table 3 below. After, no ,. The time until the precipitation of the radim, that is, the initial generation time, was determined. Table 3 shows the results.
第 3表から判るように、 アンモニア及び E D T A · 2 N aを併用する場合には、 初期発生時間が大き く短縮 される。 また、 E D T A * 2 N aを◦ . 0 0 5モル/ β 以上添加したメ ツキ液を用いた場合には、 厚付け後のメ ツキ皮膜の外観が極めて良好であった。 As can be seen from Table 3, when ammonia and EDTA · 2Na are used together, the initial generation time is greatly reduced. In addition, when using a plating solution to which EDTA * 2Na was added in an amount of .0.05 mol / β or more, the appearance of the plating film after thickening was extremely good.
実施例 4 Example 4
下記組成メ ツキ液を調製した。
o p d c δ 2 〇 . 0 1モル z s o N H2 C H2 C H2 N H2 0. 08モル/ S oチォジグリ コール酸 2 0 nig/ δ The following composition plating solution was prepared. opdc δ 2 〇. 0 1 mol zso NH 2 CH 2 CH 2 NH 2 0.08 mol / S o-thiodiglycolic acid 20 nig / δ
o N a Η2 Ρ 02 · Η2 0 0. 0 6モル o N a Η 2 Ρ 02 · Η 2 0 0.0 6 mol
このメ ツキ液を用いて、 液温 6 0。Cで銅板上にメ ツキ を行なった。 メ ツキ液の p Hは 1 1. 0であった。 その 結果析出速度は、 1 , 4 1 mZhrであり、 析出量と時 間との間に直線関係が認められ、 自己触媒析出であるこ とが確認された。 6時間連続してメ ツキを行ない厚付け を行なった結果、 得られたメ ツキ皮膜の外観は良好であ つた。 この試料を J I S — Z— 2 248に準じて曲げ試 験を行なったところ、 異状はなく 、 メ ツキ皮膜の密着性 は良好であった。 The temperature of the solution was 60 using this plating solution. C was plated on a copper plate. The pH of the plating solution was 11.0. As a result, the deposition rate was 1,41 mZhr, and a linear relationship was observed between the amount of deposition and the time, confirming that autocatalytic deposition was performed. As a result of performing plating for 6 hours continuously and performing thickening, the appearance of the obtained plating film was good. A bending test was performed on this sample in accordance with JIS-Z-2248, and there was no abnormality and the adhesion of the plating film was good.
また、 上記メ ツキ液を 9 0てに加熱してもメ ツキ液の 分解が生じることはなく 、 また 2 5 °Cで 4力月開放保存 した場合にもメ ツキ液の分解は生じなかった。 Further, even when the above plating solution was heated to 90 °, the plating solution did not decompose, and the plating solution did not decompose even when stored at 25 ° C. for 4 months. .
実施例 5 Example 5
実施例 4に示すメ ツキ液を下記第 4表に示す各 p H値 に H C S で調整し、 液温 6 0 で、 銅板上に 1 μ m厚に メ ツキ皮膜を形成させた。 得られた各メ ツキ皮膜につい て、 実施例 2と同様にして、 メ ツキ外観の観察及びハン ダ付け性試験を行なった。 結果を第 4表に示す。
第 4 The plating solution shown in Example 4 was adjusted to the respective pH values shown in Table 4 below with HCS, and a plating film having a thickness of 1 μm was formed on a copper plate at a solution temperature of 60. For each of the obtained plating films, the appearance of the plating and the solderability test were performed in the same manner as in Example 2. The results are shown in Table 4. the 4th
実施例 6 Example 6
下記組成メ ツキ液を調製した。 The following composition plating solution was prepared.
o p d C δ 2 0. 0 1 モル/ β ο ァ ミ ン化合物' χ· 0. 0 8モル/ S ο チォジグリ コール酸 2 0 mgZ S opd C δ 2 0. 0 1 mol / beta o § Mi emissions compounds' χ · 0. 0 8 mol / S o Chiojiguri cholate 2 0 MGZ S
o N a H2 P 0 a · Η 2 0 0. 0 6モルノ 2 o N a H 2 P 0 a · Η 2 0 0. 0 6 Moruno 2
ァ ミ ン化合物としては、 ジメ チルァ ミ ン、 ジメ チル ェチルァ ミ ン、 メ チレ ンジァ ミ ン、 テ ト ラメ チ レ ンジ ァ ミ ン、 ジエチレ ン ト リ ア ミ ン、 ペンタエチレ ンへキ
サ ミ ン、 N—ヒ ドロキシエチレ ンジア ミ ン三酢酸、. グ リ シン、 イ ミ ダゾリ ン、 及び 2—ベンジルー 2—イ ミ ダゾリ ンを各々単独で用いた。 The dimethylamines include dimethylamine, dimethylethylamine, methylylenediamine, tetramethylethylenediamine, diethyltriamine, and pentaethyleneimide. Samin, N-hydroxyethylenediamine triacetic acid, glycine, imidazoline, and 2-benzyl-2-imidazoline were used alone.
これらのメ ツキ液を塩酸で p H 8に調整し、 液温 6 〇 。(：で銅扳上にメ ツキを行なった。 その結果、 密着性及び 外観ともに良好な皮膜が形成された。 また得られたメ ッ 千皮膜にはクラックがなく 、 ハンダ付け性が良好であつ た。 更に、 上記各メ ツキ液について、 加熱時の安定性及 び保存安定性を調べたところ良好な安定性を示した。 These plating solutions were adjusted to pH 8 with hydrochloric acid, and the temperature of the solution was 6 ml. (: Plating was performed on the copper foil. As a result, a film with good adhesion and appearance was formed. The obtained metal coating had no cracks and good solderability. Further, the stability of each of the above-mentioned plating liquids during heating and storage stability was examined, and as a result, good stability was shown.
実施例 7 Example 7
下記組成のメ ツキ液を調製した。 A plating solution having the following composition was prepared.
o P d C δ 2 0. 0 1モル/ S o P d C δ 20.0 1 mol / S
o N H2 C H2 C H2 N H2 0. 08モル 2 o NH 2 CH 2 CH 2 NH 2 0.08 mol 2
o硫黄含有有機化合物※ 2 Oig/ S oSulfur-containing organic compound * 2 Oig / S
o N a H2 P 02 ♦ H2 0 0. 0 6モル ZS o N a H 2 P 02 ♦ H 2 0 .0 6 mol ZS
硫黄含有有機化合物と し ては、 HSCH2 COOH, HSCH 2 COOH,
を 各 々
単独で用 い た
これらのメ ツキ液を塩酸で p H 8に調整し、 液温 6 〇 °Cで銅板上にメ ツキを行なった。 その結果、 密着性及び 外観ともに良好な皮膜が形成された。 また得られたメ ッ キ皮膜はクラックがなく 、 ハンダ付け性が良好であった。 更に、 上記各メ ツキ液について、 加熱時の安定性及び保 存安定性を調べたところ良好な安定性を示した。 Each Used alone The plating solution was adjusted to pH 8 with hydrochloric acid, and plating was performed on a copper plate at a solution temperature of 6 ° C. As a result, a film having good adhesion and appearance was formed. The obtained paint film was free of cracks and had good solderability. Further, the stability of the above-mentioned plating liquids during heating and storage stability were examined, and good stability was shown.
実施例 8 Example 8
下記組成のメ ツキ液を調製した。 A plating solution having the following composition was prepared.
o P d C δ a 0. 0 1モル Ζ β o P d C δ a 0.0 1 mol Ζ β
o N H2 C Η2 C Η2 Ν Η2 0. 08モルノ 2 o NH 2 C Η 2 C Η 2 Ν Η 2 0.08 Morno 2
οチォジグリ コール酸 2 0 rag/ S ο Thiodiglycol cholic acid 20 rag / S
o還 元 剤 ·χ· ◦ . 0 6モルノ S o Reducing agent · χ · ◦. 6 Morno S
還元剤と しては、 ジメチルァ ミ ンボラ ン、 イ ソプロ ピルァ ミ ンボラ ン、 モルホリ ンボラ ン及び水素化ホゥ 素ナ ト リ ウムを各々単独で用いた。 As the reducing agent, dimethylamine, isopropylamine, morpholine and sodium borohydride were used alone.
これらのメ ツキ液を塩酸で p H 8に調整し、 液温 6 0 °Cで銅板上にメ ツキを行なった。 その結果、 密着性及び 外観ともに良好な皮膜が形成された。 また得られたメ ッ キ皮膜はクラックがなく、 ハンダ付け性が良好であった。 更に、 上記各メ ツキ液について、 加熱時の安定性及び保 存安定性を調べたところ良好な安定性を示した。 The plating solution was adjusted to pH 8 with hydrochloric acid, and plating was performed on a copper plate at a solution temperature of 60 ° C. As a result, a film having good adhesion and appearance was formed. The obtained paint film was free of cracks and had good solderability. Further, the stability of the above-mentioned plating liquids during heating and storage stability were examined, and good stability was shown.
施例 9
下記の配合組成のメ ツキ液を調製した Example 9 A plating solution having the following composition was prepared.
P d C δ 2 〇 . 0 1モル Z S P d C δ 2 〇. 0 1 mol Z S
N i C δ 2 · 6 H2 0 下記変量※ N i C δ 2 · 6 H 2 0 following variables ※
28%ア ンモニア水 20 0 mS / S 28% ammonia water 200 mS / S
チォジグリ コール酸 2 0mg/ S Thiodiglycolic acid 20 mg / S
N a H2 P 0 a · Η2 0 0. 08モル ZS N a H 2 P 0 a · Η 2 0 0. 08 mol ZS
N i C S 2 * 613：2 0は 0. 0 0 5、 0. 0 1、 0. 0 2、 0. 0 5、 0. 1及び 0. 2モル の 6 通りに変化させた。 Ni CS 2 * 613: 20 was changed in six ways: 0.005, 0.01, 0.02, 0.05, 0.1 and 0.2 mol.
得られたメ ツキ液を用いて、 液温 4 ◦ Cで銅板に 1時間 メ ツキを行なった。 メ ツキ液中の N i と P dの比率と析出 物中の N i量との関係を第 2図に示す。 第 2図から明らか な様に、 メ ツキ液中の N i と P dの比を調整することによ り、 任意の組成の析出物が得られることが判る。 また、 得 られた析出物の外観は良好であり、 J I S — Z— 2 248 に準じて曲げ試験を行なった結果、 すべての試料について 異状が生じることはなく 、 密着性は良好であった。 Using the obtained plating solution, plating was performed on the copper plate at a liquid temperature of 4 ° C. for 1 hour. Figure 2 shows the relationship between the ratio of Ni and Pd in the plating solution and the amount of Ni in the precipitate. As is clear from FIG. 2, it can be seen that a precipitate having an arbitrary composition can be obtained by adjusting the ratio of Ni and Pd in the plating solution. Further, the appearance of the obtained precipitate was good, and as a result of performing a bending test according to JIS-Z-2248, no abnormality occurred in all samples, and the adhesion was good.
更に、 上記メ ツキ液の安定性を調べるために、 9 0 °Cへ の加熱、 2 5。Cでの密閉保存、 及び 2 5ででの開放保存を 行なった結果を第 5表に示す。
5 Further, to examine the stability of the plating solution, heating to 90 ° C, 25. Table 5 shows the results of closed storage in C and open storage in 25. Five
また、 比較と して、 チォジグリ コール酸を含有せず、 他 の成分は上記メ ツキ液の組成と同様なメ ツキ液 For comparison, thiodiglycolic acid was not contained, and the other components contained the same plating solution as the above-mentioned plating solution.
(N i C δ 2 · 6 Η2 0は 0. 1モル / 2 ) を用いて保存 試験をを行なった結果、 25。Cで保存すると約 1時間で液 の分解を生じ、 40。Cでは 5分以内に液の分解を生じた。 (N i C δ 2 · 6 Η 20 is 0.1 mol / 2). When stored at C, decomposition of the solution occurs in about 1 hour. C decomposed within 5 minutes.
以上の結果から、 本発明メ ツキ液が高温での安定性及び 常温での長期保存性に優れたものであることが判る。 尚、 開放保存では、 4〜 7 日間で液の分解を生じたが、 これは 従来のメ ツキ液に比して極めて優れた結果である。 また、
この開放保存によるメ ツキ液の分解は、 アンモニアの揮発 に起因するものであり、 適宜アンモニアを補給することに より、 長時間の開放保存も可能である。 From the above results, it can be seen that the plating solution of the present invention is excellent in stability at high temperatures and long-term storage at room temperature. In addition, in the case of open storage, the solution was decomposed in 4 to 7 days, which is an excellent result compared to the conventional plating solution. Also, The decomposition of the plating solution due to the open storage is caused by the volatilization of the ammonia, and a long-time open storage is possible by appropriately supplementing the ammonia.
実施例 1 ◦ Example 1 ◦
下記組成のメ ツキ液を調製した。 A plating solution having the following composition was prepared.
P d C β a 0. 0 1モル Ζ δ P d C β a 0.0 1 mol Ζ δ
N i C δ a ♦ 6 H2 0 0. 1モル N i C δa ♦ 6 H 2 0 0.1 mol
28%ア ンモニア水 200 ϋΐβΖβ 28% ammonia water 200 ϋΐβΖβ
チォジグリ コール酸 20 nig/ δ Thiodiglycolic acid 20 nig / δ
N a Η 2 P 02 ♦ H 2 0 N a Η 2 P 02 ♦ H 2 0
又は N a B H4 0. 08モルノ2 このメツキ液を用いて、 液温 40でで銅板上にメ ツキを 行なった場合のメ ツキ時間と析出量との関係第 3図に示す。 尚、 図中、 〇印は、 N a H2 P 02 · H2 0を用いた場合、 △印は、 N a B H4 を用いた場合の結果を示す。 第 3図か ら N a H2 P 0 a ♦ H2 0を用いた場合には、 析出速度は 1. 4 Dig/cm2 ♦ hrであり、 N a B H4 を用い場合には、 析出速度は 1. 7nigZcin2 * hrであって、 いずれの場合に もメ ツキ時間と析出量との間に直線関係が認められ、 自己 触媒的析出であることが判る。 尚、 析出物中の N i量は、 N a H2 P 0 ♦ H2 0を用いた場合には、 約 30重量％ であり、 N a B H 4 を用いた場合には、 約 35重量％であ
つた。 Or with N a BH 4 0. 08 Moruno 2 This plated solution, shown in FIG. 3 the relationship between the main luck time and the amount of precipitated when subjected to main luck on a copper plate with a liquid temperature of 40. In the figure, .smallcircle, when using N a H 2 P 02 · H 2 0, △ mark shows the results obtained by using the N a BH 4. When using the Figure 3 or al N a H 2 P 0 a ♦ H 2 0 , the deposition rate is 1. 4 Dig / cm 2 ♦ hr , when using N a BH 4 is precipitation rate Is 1.7 nigZcin 2 * hr. In each case, a linear relationship was observed between the plating time and the amount of deposition, indicating that the deposition was autocatalytic. Incidentally, N i of precipitates, when using N a H 2 P 0 ♦ H 2 0 is about 30 wt%, in the case of using N a BH 4 is about 35 wt% In I got it.
実施例 1 1 Example 1 1
下記の配合組成のメ ツキ液を調製した A plating solution having the following composition was prepared.
P d C δ 2 0， 0 1 モル Z S P d C δ 20, 0 1 mol Z S
N i C β a · 6 H 2 0 0 . モル Ζ β N i C β a · 6 H 2 0.
2 8 %アンモニア水 2 0 0 m<3 / δ 2 8% ammonia water 200 m <3 / δ
硫黄含有有機化合物※ 2 0 rag/ δ Organic compounds containing sulfur * 20 rag / δ
N a H 2 P 0 2 ， H 2 0 0 . 0 8モル Ζ S N a H 2 P 0 2, H 2 0 0. 0 8 mol Zeta S
硫黄含有有機化合物と しては、 チォジグリ コール酸 チォジプロ ピオン酸及び 2—メルカプトべンゾチアゾ ールの 3種類を用いた。 As the sulfur-containing organic compound, three kinds of thiodiglycolic acid, thiodipropionic acid and 2-mercaptobenzothiazole were used.
このメ ツキ液を用いて、 液温を変化えて銅板上に 1時間 メ ツキを行なった場合の液温と析出速度との関係を第 4図 に示す。 また、 液温と析出物中の N i 量との関係を第 5図 に示す。 尚、 図中、 〇印は、 チォジグリ コール酸を用いた 場合、 △印は、 チォジプロ ピオン酸を用いた場合、 □印は 2—メルカプ トべンゾチアゾールを用いた場合の結果を示 す。 以上の結果から、 液温が高い程メ ツキ速度が増加し、 また折出物中の N 1量が増加する傾向にあることが判る。 尚、 得られたメ ツキ皮膜は、 チォジグリ コール酸、 チォジ プロ ピオン酸及び 2 —メルカプトベンゾチアゾールのいず れを用いた場合にも良好な外観であった。
実施例 1 2 Fig. 4 shows the relationship between the liquid temperature and the deposition rate when plating was performed on a copper plate for 1 hour by changing the liquid temperature using this plating liquid. Fig. 5 shows the relationship between the liquid temperature and the amount of Ni in the precipitate. In the figures, the symbol 〇 indicates the results when thiodiglycolic acid was used, the symbol △ indicates the results when thiodipropionic acid was used, and the symbol □ indicates the results when 2-mercaptobenzothiazole was used. From the above results, it can be seen that the higher the liquid temperature, the higher the plating speed and the higher the amount of N 1 in the deposit. Incidentally, the obtained paint film had a good appearance when any of thiodiglycolic acid, thiodipropionic acid and 2-mercaptobenzothiazole was used. Example 1 2
下記組成のメ ツキ液を調製した A plating solution having the following composition was prepared.
P d C δ a 0 . 0 1 モル S P d C δ a 0.01 .1 mol S
N i C δ a · 6 H 2 0 0 . 1 モルノ S N i C δ a · 6 H 2 0 0. 1 Moruno S
N H 2 C H 2 C H 2 N H 2 〇 . 0 8モル/^ NH 2 CH 2 CH 2 NH 2 〇. 0 8 mol / ^
チォジグリ コール酸 2 0 mg/ δ Thiodiglycolic acid 20 mg / δ
N a E P 0 2 · H 2 0 0 . 0 8モル Z S N a EP 0 2 · H 2 0 0. 0 8 mol ZS
このメ ツキ液を用いて、 液温 4 0でで銅板に 1時間メ ッ キを行なった。 その結果析出物中の N i量は約 3 0重量 であり、 得られた析出物の外観、 密着性は共に良好であつ た。 また上記メ ツキ液を 9 0 に加熱してもメ ツキ液の分 解が生じることはなく 、 また 2 5 で 4ヶ月間開放保存し た場合にもメ ツキ液の分解は生じなかった。 Using this plating solution, a copper plate was plated at a solution temperature of 40 for 1 hour. As a result, the amount of Ni in the precipitate was about 30% by weight, and the appearance and adhesion of the obtained precipitate were both good. When the above plating solution was heated to 90, the plating solution did not decompose, and the plating solution did not decompose even when stored at 25 for 4 months.
実施例 1 3 Example 13
実施例 1 2に示すメ ツキ液を下記第 6表に示す各 p H値 に H C S 及び N a 0 Hで調製し、 液温 4 0 で銅板上に 1 m厚にメ ツキ皮膜を形成させた。 得られた各メ ツキ皮膜 について、 メ ツキ皮膜の状態及びハンダ付け性試験、 並び にメ ツキ速度の測定を行なった。 結果を第 6表に示す。
6 The plating solution shown in Example 12 was prepared at each pH value shown in Table 6 below with HCS and Na0H, and a plating film having a thickness of 1 m was formed on a copper plate at a solution temperature of 40. . With respect to each of the obtained paint films, the condition of the paint film and the solderability test, and the plating speed were measured. The results are shown in Table 6. 6
実施例 14 Example 14
下記組成のメ ツキ液を調製した A plating solution having the following composition was prepared.
P d C δ 2 0. 0 1モル/ S P d C δ 2 0.0 1 mol / S
N i C δ 2 ♦ 6 H2 0 0. モル Z β N i C δ 2 ♦ 6 H 2 0 0.mol Z β
ァ ミ ン化合物※ 0. 08モル/ S Amine compound * 0.08 mol / S
チォジグリ コール酸 2 0 nig/ δ Thiodiglycolic acid 20 nig / δ
N a H2 P 02 · H2 0 〇 . 0 6モル/ δ NaH 2 P 02H 2 0 〇 .0 6 mol / δ
ァ ミ ン化合物と しては、 ジメチルァ ミ ン、 ジメチル ェチルァ ミ ン、 メ チレ ンジァ ミ ン、 テ ト ラメ チ レ ンジ
ァ ミ ン、 ジエチ レ ン ト リ ア ミ ン、 ペンタエチレ ンへキ サミ ン、 N—ヒ ドロキシエチレンジア ミ ン三酢酸、 グ リ シン、 イ ミ ダゾリ ン、 及び 2—べンジルー 2—イ ミ ダゾリ ンを各々単独で用いた。 Diamines such as dimethylamine, dimethylethylamine, methylamine, and tetramethylamine Amide, diethylenamine, pentaethylenehexamine, N-hydroxyethylenediamintriacetic acid, glycine, imidazoline, and 2-benzyl-2-imine Dazolin was used alone.
これらのメ ツキ液を塩酸で p H 8に調整し、 液温 6〇て で銅板上にメ ツキを行なった。 その結果、 密着性及び外観 ともに良好な皮膜が形成された。 また得られたメ ツキ皮膜 はクラックがなく 、 ハンダ付け性が良好であった。 更に、 上記各メ ツキ液について、 加熱時の安定性及び保存安定性 を調べたところ良好な安定性を示した。 These plating solutions were adjusted to pH 8 with hydrochloric acid, and plated at 6 ° C. on a copper plate. As a result, a film having good adhesion and appearance was formed. The resulting paint film was free of cracks and had good solderability. Further, the stability of each of the above plating liquids upon heating and storage stability were examined, and good stability was shown.
実施例 1 5 Example 15
下記組成のメ ツキ液を調製した。 A plating solution having the following composition was prepared.
P d C δ 2 0 0 1モル/ δ P d C δ 2 0 0 1 mol / δ
N i C δ a ♦ 6 H2 0 〇 1モル S N i C δa ♦ 6 H 2 0 〇 1 mol S
N H2 C H2 C H2 N H2 0 08モル / S NH 2 CH 2 CH 2 NH 2 0 08 mol / S
硫黄含有有機化合物※ 2 〇 ig/ δ Organic compounds containing sulfur * 2 ※ ig / δ
N a H2 P 0 a ♦ H2 0 0. 06モル/ S 硫黄含有有機化合物と して は、 HSCH2 COOH, SH N a H 2 is set to P 0 a ♦ H 2 0 0. 06 mol / S sulfur-containing organic compounds, HSCH 2 COOH, SH
, HOOC CH2 CH2 S CH2 CH2 COOH,
( C H3 ) 2 S 2 ， を 各 々
, HOOC CH 2 CH 2 S CH 2 CH 2 COOH, (C H3) 2 S 2, respectively
単独で用 い た Used alone
これらのメ ツキ液を塩酸で p H 8に調整し、 液温 6〇°C で銅板上にメ ツキを行なった。 その結果、 密着性及び外観 ともに良好な皮膜が形成された。 また得られたメ ツキ皮膜 はクラックがなく 、 ハンダ付け性が良好であった。 更に、 上記各メ ツキ液について、 加熱時の安定性及び保存安定性 を調べたところ良好な安定性を示した。 The plating solution was adjusted to pH 8 with hydrochloric acid, and plating was performed on a copper plate at a solution temperature of 6 ° C. As a result, a film having good adhesion and appearance was formed. The resulting paint film was free of cracks and had good solderability. Further, the stability of each of the above plating liquids upon heating and storage stability were examined, and good stability was shown.
実施例 16 Example 16
下記組成のメ ツキ液を調製した。 A plating solution having the following composition was prepared.
P d C δ a 0. 0 1モル P d C δ a 0.0 1 mol
N i C δ 2 · 6 Η2 0 0. 1モル ZS N i C δ 2 6 6 2 0 0.1 mol ZS
N H2 C H2 C H2 N H2 0. 〇 8モル Ζδ NH 2 CH 2 CH 2 NH 2 0. 〇 8 mol Ζδ
チォジグリ コール酸 20 nig/ δ Thiodiglycolic acid 20 nig / δ
還 元 剤※ 0. 06モル S Reducing agent * 0.06 mol S
還元剤と しては、 ジメチルァ ミ ンボラ ン、 イ ソプロ ピルア ミ ンボラ ン、 モルホ リ ンボラ ン及び水素化ホウ 素ナ ト リ ゥムを各々単独で用いた。 Dimethylamine, isopropylamine, morpholine, and sodium borohydride were used alone as the reducing agents.
これらのメ ツキ液を塩酸で ρ Η 8に調整し、 液温 6〇て で銅板上にメ ツキを行なった。 その結果、 密着性及び外観 ともに良好な皮膜が形成された。 また得られたメ ツキ皮膜
はクラックがなく 、 ハンダ付け性が良好であった。 更に、 上記各メ ツキ液について、 加熱時の安定性及び保存安定性 を調べたところ良好な安定性を示した。
These plating liquids were adjusted to ρΗ8 with hydrochloric acid, and plated at 6 ° C. on a copper plate. As a result, a film having good adhesion and appearance was formed. The obtained plating film Had no cracks and good solderability. Further, the stability of each of the above plating liquids upon heating and storage stability were examined, and good stability was shown.
Claims
請求の範囲 The scope of the claims
① a ) パラ ジウム化合物 0. 000 1〜 0. 5モル ① a) Palladium compound 0.001 to 0.5 mol
b ) アンモニア及びア ミ ン化合物の少なく とも 1種 b) at least one of ammonia and an amine compound
〇. 00 1〜8モル （2 〇. 00 1 to 8 mol (2
c ) 二価の硫黄を含有する有機化合物 1〜 50 OmgZS 、 並びに c) divalent sulfur-containing organic compound 1-50 OmgZS, and
d ) 次亜リ ン酸化合物及び水素化ホウ素化合物の少なく とも 1種◦ , 005〜 1モル Ζβ d) At least one of hypophosphorous acid compound and borohydride compound ◦, 005 to 1 mol Ζβ
を含む水溶液からなることを特徵とするパラ ジウム系無 電解メ ツキ液。 A palladium-based electroless plating solution comprising an aqueous solution containing
② ァ ミ ン化合物がモノア ミ ン類、 ジァ ミ ン類、 ポリア ミ ン類、 ァ ミ ノ酸類及びィ ミ ダゾリ ン類である請求の範囲 第 1項に記載のパラジゥム系無電解メ ツキ液。 (2) The palladium-based electroless plating solution according to claim 1, wherein the amide compound is a monoamine, a diamine, a polyamine, an amic acid, or an imidazoline. .
③ ァ ミ ン化合物がジァ ミ ン類及びポリ ァ ミ ン類である請 求の範囲第 1項に記載のパラジゥム系無電解メ ツキ液。 (3) The palladium-based electroless plating solution according to claim 1, wherein the amide compound is a diamine or a polyamine.
④ ア ミ ン化合物がェチレ ンジア ミ ン及びジエチレ ン ト リ ア ミ ンである請求の範囲第 1項に記載のパラジウム系無 電解メ ツキ液。 4. The palladium-based electroless plating solution according to claim 1, wherein the amine compound is ethylenediamine and diethyltriamine.
⑤ 二価の硫黄を含有する有機化合物がメルカブタ ン類、 スルフィ ド類、 ジスルフィ ド類、 チアゾール類、 ！ ： i
及び !1 ； の少なく とも 1種である請求の範囲第 S 有機 Organic compounds containing divalent sulfur are mercaptans, sulfides, disulfides, thiazoles,! : I And at least one kind of! 1;
1項に記載のパラジゥム系無電解メ ツキ液。 2. The palladium electroless plating solution according to item 1.
⑥ ' 二価の硫黄を含有する有機化合物がスルフィ ド類及び ジスルフィ ド類の少なく とも 1種である請求の範囲第 1 項に記載のパラジゥム系無電解メ ツキ液。 The palladium-based electroless plating solution according to claim 1, wherein the organic compound containing divalent sulfur is at least one of a sulfide and a disulfide.
⑦ p Hが約 5〜約 1 0である請求の範囲第 1項に記載の パラジゥム系無電解メ ツキ液。 The palladium-based electroless plating solution according to claim 1, wherein the pH is from about 5 to about 10.
⑧ a ) ノ、。ラジウム化合物 0. 000 1〜 0. 5モル ZS b ) ニッケル化合物 0. 00 1〜 1モル ⑧ a) No. Radium compound 0.000 1-0.5 mol ZS b) Nickel compound 0.001 1-1 mol
c ) ア ンモニア及びア ミ ン化合物の少なく とも 1種 c) At least one of ammonia and amine compounds
0. 00 1〜8モル/ S 0.00 1-8 mol / S
d ) 二価の硫黄を含有する有機化合物 1〜 50◦ nigZ 2 並びに d) Organic compounds containing divalent sulfur 1 to 50 ° nigZ 2 and
e ) 次亜リ ン酸化合物及び水素化ホウ素化合物の少なく とも 1種 0. 005〜 ： [ モル/ S e) At least one of hypophosphorous acid compound and borohydride compound 0.005 ~: [mol / S
を含む水溶液からなることを特徴とするパラジゥム系無 電解メ ツキ液。 A palladium-based electroless plating solution comprising an aqueous solution containing:
⑨ ア ミ ン化合物がモノア ミ ン類、 ジァ ミ ン類、 ポリア ミ ン類、 ァ ミ ノ酸類及びィ ミ ダゾリ ン類である請求の範囲 第 8項に記載のパラジゥム系無電解メ ツキ液。 9. The palladium-based electroless plating solution according to claim 8, wherein the amine compound is a monoamine, a diamine, a polyamine, an amic acid, or an imidazoline. .
⑩ ァ ミ ン化合物がジァ ミ ン類及びポリァ ミ ン類である請
求の範囲第 8項に記載のパラジゥム系無電解メ ツキ液。 ⑪ ァ ミ ン化合物がエチレ ンジァ ミ ン及びジエチレ ン ト リ ァ ミ ンである請求の範囲第 8項に記載のパラジウム系無 電解メ ツキ液。 Check that the amine compound is a diamine or polyamine. 9. The palladium-based electroless plating solution according to claim 8. 9. The palladium-based electroless plating solution according to claim 8, wherein the diamine compound is ethylenediamine and diethyltriamine.
⑫ 二価の硫黄を含有する有機化合物がメ ルカブタ ン類、 スルフ 及び有機 Organic compounds containing divalent sulfur can be used for mercaptans, sulf
8項に記載のパラジゥム系無電解メ ツキ液。 8. The palladium electroless plating solution according to item 8.
⑬ 二価の硫黄を含有する有機化合物がスルフィ ド類及び ジスルフィ ド類の少なく とも 1種である請求の範囲第 8 項に記載のパラジゥム系無電解メ ツキ液。 9. The palladium electroless plating solution according to claim 8, wherein the organic compound containing divalent sulfur is at least one of a sulfide and a disulfide.
⑭ p Hが約 5〜約 1 1である請求の範囲第 8項に記載の パラジウム系無電解メ ツキ液。
9. The palladium-based electroless plating solution according to claim 8, wherein ⑭pH is about 5 to about 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3790128A DE3790128C2 (en) | 1986-03-04 | 1987-02-21 | Electroless plating soln. for palladium deposition |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4672786 | 1986-03-04 | ||
| JP61/46727 | 1986-03-04 | ||
| JP61/196282 | 1986-08-21 | ||
| JP19628286A JPS62124280A (en) | 1985-08-21 | 1986-08-21 | Electroless palladium plating solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1987005338A1 true WO1987005338A1 (en) | 1987-09-11 |
Family
ID=26386842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP1987/000113 WO1987005338A1 (en) | 1986-03-04 | 1987-02-21 | Palladium-base electroless plating solution |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4804410A (en) |
| DE (2) | DE3790128C2 (en) |
| WO (1) | WO1987005338A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL8900305A (en) * | 1989-02-08 | 1990-09-03 | Philips Nv | METHOD FOR MANUFACTURING A SEMICONDUCTOR DEVICE |
| JPH0828561B2 (en) * | 1991-01-18 | 1996-03-21 | 石原薬品株式会社 | Manufacturing method of printed wiring board |
| US5206055A (en) * | 1991-09-03 | 1993-04-27 | General Electric Company | Method for enhancing the uniform electroless deposition of gold onto a palladium substrate |
| US5219815A (en) * | 1991-09-23 | 1993-06-15 | Applied Electroless Concepts Inc. | Low corrosivity catalyst containing ammonium ions for activation of copper for electroless nickel plating |
| US5380560A (en) * | 1992-07-28 | 1995-01-10 | International Business Machines Corporation | Palladium sulfate solution for the selective seeding of the metal interconnections on polyimide dielectrics for electroless metal deposition |
| US5882736A (en) * | 1993-05-13 | 1999-03-16 | Atotech Deutschland Gmbh | palladium layers deposition process |
| DE4415211A1 (en) * | 1993-05-13 | 1994-12-08 | Atotech Deutschland Gmbh | Process for the deposition of palladium layers |
| US6800499B2 (en) * | 1999-05-28 | 2004-10-05 | National Science Council | Process for preparing a hydrogen sensor |
| JP4482744B2 (en) * | 2001-02-23 | 2010-06-16 | 株式会社日立製作所 | Electroless copper plating solution, electroless copper plating method, wiring board manufacturing method |
| US6677233B2 (en) * | 2002-01-02 | 2004-01-13 | Intel Corporation | Material deposition from a liquefied gas solution |
| US20100098863A1 (en) * | 2003-03-12 | 2010-04-22 | University Of Missouri | Process for spontaneous deposition from an organic solution |
| US20060210837A1 (en) * | 2004-04-16 | 2006-09-21 | Fuji Electric Device | Method of plating on a glass base plate, a method of manufacturing a disk substrate for a perpendicular magnetic recording medium, a disk substrate for a perpendicular magnetic recording medium, and a perpendicular magnetic recording medium |
| JP4539282B2 (en) * | 2004-04-16 | 2010-09-08 | 富士電機デバイステクノロジー株式会社 | Disk substrate for perpendicular magnetic recording medium and perpendicular magnetic recording medium using the same |
| JP4475026B2 (en) * | 2004-06-11 | 2010-06-09 | 富士電機デバイステクノロジー株式会社 | Electroless plating method, magnetic recording medium, and magnetic recording apparatus |
| JP4479528B2 (en) * | 2004-07-27 | 2010-06-09 | 富士電機デバイステクノロジー株式会社 | Method of plating on glass substrate, method of manufacturing disk substrate for magnetic recording medium using the plating method, and method of manufacturing perpendicular magnetic recording medium |
| JP4479493B2 (en) * | 2004-12-14 | 2010-06-09 | 富士電機デバイステクノロジー株式会社 | Method of plating on glass substrate and method of manufacturing magnetic recording medium using the same |
| JP4479571B2 (en) * | 2005-04-08 | 2010-06-09 | 富士電機デバイステクノロジー株式会社 | Method for manufacturing magnetic recording medium |
| US7704307B2 (en) * | 2005-07-20 | 2010-04-27 | Nippon Mining & Metals Co., Ltd. | Electroless palladium plating liquid |
| JP4844716B2 (en) * | 2005-09-27 | 2011-12-28 | 上村工業株式会社 | Electroless palladium plating bath |
| WO2008056403A1 (en) * | 2006-11-06 | 2008-05-15 | C. Uyemura & Co., Ltd. | Direct plating method and solution for palladium conductor layer formation |
| CN101448973B (en) * | 2007-02-28 | 2014-06-25 | 小岛化学药品株式会社 | Electroless pure-palladium plating solution |
| JP4117016B1 (en) * | 2007-08-15 | 2008-07-09 | 小島化学薬品株式会社 | Electroless palladium plating solution |
| JP5525762B2 (en) * | 2008-07-01 | 2014-06-18 | 上村工業株式会社 | Electroless plating solution, electroless plating method using the same, and method for manufacturing wiring board |
| JP5297171B2 (en) * | 2008-12-03 | 2013-09-25 | 上村工業株式会社 | Electroless nickel plating bath and electroless nickel plating method |
| JP4511623B1 (en) * | 2009-05-08 | 2010-07-28 | 小島化学薬品株式会社 | Electroless palladium plating solution |
| EP2444522B1 (en) * | 2010-10-21 | 2017-04-05 | Rohm and Haas Electronic Materials LLC | Stable nanoparticles for electroless plating |
| EP2581470B1 (en) * | 2011-10-12 | 2016-09-28 | ATOTECH Deutschland GmbH | Electroless palladium plating bath composition |
| JP6231982B2 (en) | 2012-07-13 | 2017-11-15 | 東洋鋼鈑株式会社 | Electroless gold plating method and gold plating coating material |
| CN104428934B (en) * | 2012-07-13 | 2017-12-08 | 东洋钢钣株式会社 | Separator for fuel battery, cell of fuel cell, the manufacture method of fuel cell pack and separator for fuel battery |
| US20150024123A1 (en) * | 2013-07-16 | 2015-01-22 | Rohm And Haas Electronic Materials Llc | Catalysts for electroless metallization containing iminodiacetic acid and derivatives |
| KR101617654B1 (en) * | 2013-08-23 | 2016-05-03 | 숭실대학교 산학협력단 | Manufacturing method of palladium thin films using electroless-plating |
| CA2928616A1 (en) | 2013-10-28 | 2015-05-07 | Toyo Kohan Co., Ltd. | Alloy plate coated material and method of producing alloy plate coated material |
| US9603258B2 (en) * | 2015-08-05 | 2017-03-21 | Uyemura International Corporation | Composition and method for electroless plating of palladium phosphorus on copper, and a coated component therefrom |
| JP7149061B2 (en) * | 2017-10-06 | 2022-10-06 | 上村工業株式会社 | Electroless palladium plating solution |
| JP7185999B2 (en) | 2017-10-06 | 2022-12-08 | 上村工業株式会社 | Electroless palladium plating solution |
| JP7407644B2 (en) * | 2020-04-03 | 2024-01-04 | 上村工業株式会社 | Palladium plating solution and plating method |
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|---|---|---|---|---|
| JPS5337045B2 (en) * | 1975-06-24 | 1978-10-06 |
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| GB1129984A (en) * | 1964-10-30 | 1968-10-09 | Usa | Electroless deposition of nickel-phosphorus alloys |
| US3418143A (en) * | 1967-08-15 | 1968-12-24 | Burroughs Corp | Bath for the electroless deposition of palladium |
| US3515563A (en) * | 1967-12-28 | 1970-06-02 | Photocircuits Corp | Autocatalytic metal plating solutions |
| CH567223A5 (en) * | 1971-10-13 | 1975-09-30 | Bbc Brown Boveri & Cie | |
| JPS5337045A (en) * | 1976-09-17 | 1978-04-05 | Asahi Glass Co Ltd | Antireflection plastic lens |
| DE2841584A1 (en) * | 1978-09-25 | 1980-04-03 | Siemens Ag | Baths for electroless palladium deposition - contg. di:aryl-thio:formazan as stabiliser and benzene deriv. as accelerator |
| US4255194A (en) * | 1979-01-15 | 1981-03-10 | Mine Safety Appliances Company | Palladium alloy baths for the electroless deposition |
-
1987
- 1987-02-21 DE DE3790128A patent/DE3790128C2/en not_active Expired - Lifetime
- 1987-02-21 DE DE19873790128 patent/DE3790128T/de active Pending
- 1987-02-21 WO PCT/JP1987/000113 patent/WO1987005338A1/en active Application Filing
- 1987-02-21 US US07/128,111 patent/US4804410A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5337045B2 (en) * | 1975-06-24 | 1978-10-06 |
Also Published As
| Publication number | Publication date |
|---|---|
| US4804410A (en) | 1989-02-14 |
| DE3790128T (en) | 1988-03-31 |
| DE3790128C2 (en) | 1995-07-27 |
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